STUDIES IN CYCLOPROPANE CHEMISTRY THE REACTION OF ACID CHLORIDES WITH CYCLOPROPANE THE SYNTHESIS OF DICYCLOPROPYL KETONE By Omer E. C urtis J r . AN ABSTRACT Submitted to the School of Graduate S tud ies o f Michigan S ta te C ollege o f A griculture and Applied Science in p a r tia l f u lf illm e n t of the requirem ents fo r the degree of DOCTOR OF PHILOSOPHY Department o f Chemistry Year Approved 195£ ABSTRACT T his t h e s is d ea ls w ith se v e r a l asp ects o f the chem istry o f c y c lo ­ propane, and compounds con tain in g the cyclopropyl group. The re a c tio n o f a cid ch lo rid es w ith cyclopropane in the presence o f aluminum ch lo rid e was in v e stig a te d to determine i f t h is r e a c tio n would g iv e a convenient method fo r preparing cyclopropyl k eto n es. -chloroketon es and thereb y, Cyclopropane was found to r ea ct r e a d ily w ith acid ch lo rid e s but in stea d o f on ly a s in g le product ( i . e . , the expected T '-chloroketone) a mixture o f chloroketones was o b tain ed . In sev era l ca ses the chloroketones could be separated by d i s t i l l a t i o n in to two isom eric f r a c t io n s . The lower b o ilin g chloroketones were e a s il y de­ hydro halogenated by r e flu x in g w ith a sodium bicarbonate s o lu tio n to isopropenyl k eto n es. Infrared s p e c tr a , m elting p o in ts and mixed m elt­ in g p o in ts o f d e r iv a t iv e s , and reduction to iso p ro p y l ketones were used to prove the stru ctu re o f th e lower b o ilin g ch lorok eton es. This shows th a t one course o f the r ea c tio n i s as fo llo w s: 2 I t was a lso p o ss ib le to sep arate the isom eric chloroketones by s e le c t i v e l y dehydrohalogenating the jS -chloroketon es by r e flu x in g with a sodium bicarbonate s o lu t io n . The higher b o ilin g chloroketones proved to be the a n tic ip a te d 7 * -ch loropropyl ketones and upon dehydrohalogenation, th ey gave c y c lo ­ propyl k eto n es. fi R -C -C l + CH28 | >CH3 0 A lc la v R -G -C H2-G H 2 -C H2- C 1 CHo» N aO H % h -S-CTH f * Nc 2 The o v e r - a ll y ie ld o f chloroketones was 60-80$, t h e - a n d - i s o ­ mers being formed in about a 2:1 r a t io . The rea ctio n was stu d ied with ft= m ethyl, e t h y l, n -p rop yl, iso p r o p y l, cyclopropyl and phenyl. D icyclopropyl ketone was o f in te r e s t as an in term ediate in the preparation o f o th er d icyclop rop yl compounds. Furthermore, exam ination o f i t s absorption sp ectra and chem ical behavior was expected to give a d d itio n a l inform ation concerning the conjugation o f the cyclopropane rin g w ith the carbonyl group. The f i r s t sy n th e tic method was patterned a f t e r the known sy n th esis o f methyl cyclopropyl k e to n e . Methyl cyclopropyl ketone was condensed w ith d ie th y l carbonate to give 3-cyclop ropyl-3-k etop rop an oate. Tliis compound, on treatm ent w ith eth ylene o x id e, gave CL -cyclopropanecarbonylT '-b u tr o la c to n e . When t h is compound was trea ted with concentrated hydrochloric a c id , l,7-d ich loro-l*-h ep tan on e was obtained and was r e a d ily converted in to d icyclop rop yl ketone by sodium hydroxide. The second method in volved the b ase-catalyzed condensation o f 'Y -b utyrolacton e to dib u tyrolactone and the treatm ent w ith concentrated hydrochloric acid to give 1,7-dichloro-U -heptanone in good y ie ld . 2 ch2- ch2 H31 ch2 CH2 0 ^ ch2 NaOH Cl-C H2-C H2-C Hg-C-G H2-C H2-C H2-G1 ^CHg The stru ctu re o f d icyclop rop yl ketone was proved by the Beckmann rearrangement o f i t s oxime to N-cyclopropylcyclopropanecarboxam ide. This compound was a lso prepared from cyclopropylaxnine and cyclopropanecarbonyl c h lo r id e . The two were proved to be id e n t ic a l by m eltin g p oin t and mixed m eltin g p o in t . D icyclop rop ylcarb in ol was prepared by red u ction o f d icyclop rop yl ketone w ith lith iu m aluminum hydride. D icyclopropyl methane was pre­ pared by the W olff-K ishner red u ctio n . D icyclopropyl ketone and hydrazine furnished the hydrazone and the a z in e , a m olecule w ith four cyclopropane r in g s . Since -butyrolacton e was the s ta r tin g m aterial fo r the preparation o f d icyclop rop yl k eton e, i t s reported q u a n tita tiv e sy n th e sis from malonic e s t e r , ethylene oxide and aluminum ch lo rid e was r e in v e s tig a te d . The products o f the r e a c tio n were shown to be /$ -ch lo r o e th y l e th y l malonate and b is -/^ -c h lo r o e th y l m alonate. No *¥ -b utyrolacton e was o b ta in ed . STUDIES IN CYCLOPROPANE CHEMISTRY THE REACTION OF ACID CHLORIDES VITH CYCLOPROPANE THE SYNTHESIS OF DICYCLOPROPYL KETONE By Qmer E. C u rtis J r . A THESIS Submitted to th e School o f Graduate S tu d ies o f Michigan S ta te C o lleg e o f A griculture and Applied Science in p a r t ia l f u lf illm e n t o f the requirements fo r the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1955 ProQuest Number: 10008476 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest. ProQuest 10008476 Published by ProQuest LLC (2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 ACKNOWLEDGMENT The author wishes to express h is deep ap p reciation fo r the help and encouragement o f Doctor Harold Hart during the course of t h is in v e s t ig a tio n . -SBHHHi-S-X-iHB* -JBBHBHBKc •iHtHHHHr a TABLE OF CONTENTS Page PREFACE.................................................................................................................................... 1 PART I THE REACTION OF ACID CHLORIDES WITH CYCLOPROPANE. ............................. 2 INTRODUCTION.................................................................................................................... EXPERIMENTAL................................................................................................................. The r e a c tio n o f propionyl ch lorid e w ith cyclopropane...................... Dehydro halo genation o f l-ch loro-2-m eth yl-3-p en tan on e...................... Preparation o f l-chloro-2-m ethyl-3-p entan one from d ieth ylk eton e Hydrogenation o f 2-rneth y l-l-p e n te n e -3 -o n e ....................................... Dehydrohalogenation o f 6-chloro-3-hexanone............................................ The r e a c tio n o f iso b u ty ry l ch lorid e with cyclopropane.................... Dehydrohalogenation o f l-c h lo r o -2 ^ -d im eth yl-3-p en tan on e.............. hydrogenation o f 2 ,l 4-d im eth y l-l-p e n ten e- 3 -o n e ..................................... Dehydrohalogenation o f 6-chloro-2-m ethyl-3-hexanone......................... The r e a c tio n o f n -b u tyryl ch lorid e with cyclopropane...................... Dehydrohalo genation o f l-ch lo ro -b -h ep ta n o n e.......................................... hydrogenation o f 2 -m eth y l-l-h ex en e-3 -o n e................................................ Preparation o f n -propylcyclopropyl ketone from cyclopropanecarbonyl c h lo r id e .............................................................................................. Preparation o f 2-eth y lcyclop en tan on e......................................................... R eaction o f a c e ty l ch lo rid e with cyclopropane........................................ Preparation o f 3-m ethyl-3-butene-2-one from methyl e th y l ketone Hydrogenation o f 3-m ethyl-3-butene-2-one (from a c e ty l ch lo rid e and cyclop rop an e)............................................................ Delydrohalogenation o f 5-chloro-2-pentan© ne...................................... The r e a c tio n o f benzoyl ch lorid e with cyclopropane....................... Preparation o f f i -chloroisobutyrophenone from propiophenone. . . Dehydrohalogenation o f -chloroisobutyrophenone................................. Hydrogenation o f cL -roethylacrylophenone..................................................... Dehydrohalogenation o f T'-chloro-n-butyrophenone................................. R eaction o f cyclopropanecarbonyl ch lorid e w ith c y c lo p r o p a n e .... Hydrogenation o f cyclop rop yl isopropenyl k eto n e ................................. Dehydrohalogenation o f the chloroketone from cyclopropane­ carbonyl ch lo rid e and cyclopropane........................................................... R eaction o f n-propylcyclopropyl ketone w ith hydrogen ch lo rid e in the presence o f aluminum c h lo r id e ....................................................... 2 6 6 8 8 9 10 10 11 12 12 13 lij 15 15 16 17 18 19 19 20 21 21 22 22 23 2k 25 25 Page TABLE OF CONTENTS - Continued The re a ctio n o f propionyl ch lo rid e w ith cyclopropane in the ................. ...................................... presence o f f e r r i c c h lo r id e R eaction o f propionyl ch lo rid e w ith cyclopropane in n itr o methane........................................................................................... The re a ctio n o f phosgene w ith cyclopropane.......................................... A n a ly se s................................................................................................................... M elting p o in ts .................................................................................... 26 26 27 28 28 DISCUSSION............................ 29 I . Proof o f Structure o f the Lower B o ilin g C hloroketones.................. 29 Propionyl ch lo rid e and cyclopropane.......................................... Isob u tyryl ch lo rid e and cyclopropane........................................ A cetyl ch lo rid e and cyclopropane................................................. Benzoyl ch lo rid e and cyclopropane............................................... n-Butyryl fchloride and cy clo p ro p a n e...-.................................... Cyclopropanecarbonyl ch lorid e and cyclopropane................... 29 31 31 31 32 32 I I . Proof o f Structure fo r the Higher B o ilin g Chloroketones From Acid C lilorides and Cyclopropane............................................................... 3^ I I I . N otes on Experimental Procedure............................................................... 35 a. b. c. d. e. f. a. b. c. d. Dehydrohalogenation of j$ -ch lo ro k eto n es.................................. Reduction o f the unsaturated k eto n es........................................ Chlorine a n a ly sis o f ch lorok eton es............................................. De hydrohalo genation o f > -chloropropyl k eto n es..................... 35 38 38 38 PART I I SYNTHESIS AND PROPERTIES OF DICYCLOPROPYL KETONE..................................... 39 INTRODUCTION............................................................................................................... 39 EXPERIMENTAL............................................................................ .................................. The preparation of a t -a c e t y l- y -b u ty ro la cto n e ............................... I4.3 The preparation o f e th y l 3-cyclop rop yl-3-k etop ropan oate k3 The preparation o f 2 2 / c A j .- J CH2-CH£ IC1 I ^ C lJ L c H a CHa < ■ ■ ■ N- — -------------- C H a J - C H g - C H g - C H a C l Although t h is i s a s a tis fa c t o r y method fo r the methyl k etone, a p p lica ­ t io n to o th er a lk y l groups would require a c y la c e tic e s te r s which are n o t r e a d ily a v a ila b le . 6 EXPERIMENTAL The R eaction o f Propionyl Chloride w ith Cyclopropane The fo llo w in g i s ty p ic a l of the general procedure used fo r the r e a c tio n o f se v e r a l a cid ch lo rid es w ith cyclopropane. In a two l i t e r three-necked f la s k , f i t t e d w ith an ad d ition fu n n e l, thermometer and a m ercury-sealed s t ir r e r there was placed 266 g . (2 m oles) o f aluminum ch lo rid e and 800 m l. o f chloroform . The mixture was cooled i n an ic e b a th , and 186 g . (2 moles) o f propionyl ch lo rid e was added over a period o f f i f t e e n m in utes. The s o lu tio n was s tir r e d u n t il a l l th e aluminum ch lo rid e d is s o lv e d . The a d d itio n funnel was removed and a gas a d d itio n tube w ith a f r i t t e d g la s s d isk was in s e r te d . The ad d ition tube was connected to a mercury manometer so th a t the pressure o f the cyclopropane could be kept below the h eigh t o f the mercury in the s t ir r e r . Cyclopropane (86 g . , 2.0$ m oles) was slow ly added to the s o lu tio n so th a t i t was a l l absorbed, w ith the temperature m aintained below 2 0 °. The p ro cess was u su a lly exotherm ic. A fte r the a d d itio n o f the c y c lo ­ propane was completed the s o lu tio n was s tir r e d fo r one hour. I t was then poured slo w ly in to a m ixture o f 1$00 g. o f cracked ic e and 300 m l. o f concentrated hydrochloric a c id . The chloroform la y e r was sep arated , washed once w ith $00 m l. w ater, once w ith $00 m l. o f 10# sodium b i­ carb on ate, and again w ith $00 m l. o f w ater. then d ried over calcium ch lo rid e a t 0 ° . The chloroform s o lu tio n was The so lv e n t was removed in vacuo, m aintaining the p ot temperature below U0°. The resid u e was d i s t i l l e d 7 in vacu o. y ie ld in g 196 g . (73$) o f a m ixture o f chloroketones b o ilin g a t ^0-60° a t 5 mm. The product was r e fr a c tio n a ted through an e f f i c i e n t column and th ere -was obtained 105 g . (.39%) o f l-ch loro-2-m eth yl-3-p en tan on e, b .p . 1*6 a t limm., n^ t^ 1.1*31*7-1.2*353 ( l i t . v a lu e , b .p . 61*° a t 9 mm., 1.U U 07).21* Anal. C a lc 'd . fo r C6HX10C1 : C l, 26.1*. Founds C l, 2 5 .8 , 2 5 .9 . There was a lso obtained 50 g . (19$) o f 6-chloro-3-hexanon e, b .p . 5 2 -3 ° a t 3 mm., 1.1*370-1.1*395. Normant^ prepared t h is compound but does n o t d escrib e e it h e r the method o f preparation or p h y sic a l p r o p e r tie s . A n al. C alcM . fo r CgHnOCl : C l, 26.1*. Found: C l, 2 6 .0 , 2 5 .8 . The 2 ,l*-dinitrophenylhydrazones o f th ese chloroketones were p repared according to the procedure o f Johnson 26 and a f t e r r e c r y s t a lli ­ z a tio n from methyl a lc o h o l m elted a t 90-1° and 128-9° r e s p e c tiv e ly . A nal. C a lc 'd . fo r C13H16Na04Cl: C, 2*5.8; H, 1*.8; N, 1 7 .8 ; C l, 1 1 .3 . Found f o r l-ch lo ro -2 -m eth yl-3-p en tan on e-2,l*-d in itrop h en ylhydrazone: C, 1*7.0; H, 5 .1 ; N, 17.55; C l, 1 0 .2 . The a n alyses f o r the 2,U -dinitrophenylhydrazones o f the 0 -ch lorok eton es were n ot s a t is f a c t o r y . N e v e r th e le ss, th ese chloroketones gave unsaturated and satu rated k eto n es, the a n alyses and d e r iv a tiv e s o f which were s a t i s ­ fa c to r y . Found fo r 6-chloro-3-hexanone 2 ,l*-dinitrophenylhydrazone: H, 5 .0 ; N, 17.15; C l, 1 1 .1 . C, 1*6.2; 8 The fo llo w in g fo u r experim ents d ea l w ith proving th e stru ctu res o f the ch lo ro k eto n es. The same p a ttern i s fo llo w ed fo r the oth er a cid c h lo r id e s . Dehydrohalogenation o f l-chloro-2-m ethyl-3-p entan one In a £00 m l. three-necked f la s k f i t t e d w ith a r e f lu x condenser, a Harshberg s t i r r e r and an a d d itio n funnel th ere was placed 300 m l. o f water and 2£ g . o f sodium carbonate. To the r e flu x in g s o lu tio n was added 20 g. (0 .1 £ mole) o f l-chloro-2-m eth yl-3-p en tan on e; the mixture was r eflu x ed fo r f i f t e e n m in u tes, then steam d i s t i l l e d . The upper la y e r in th e d i s t i l l a t e was separated and the water la y er was extra cted once w ith e th e r . c h lo r id e . The combined organic p ortion s were dried over calcium A fter removal o f the s o lv e n t, there was obtained 8 g . (1*1$) o 25 o f 2 -m eth y l-l-p en ten e-3 -o n e , b .p . 1*0-1 a t 29 ram., n^ 1.1*263 ( l i t . v a lu e , b .p . 119° a t 7 £ l mm., n^^*^ 1.1*270) The semicarbazone was prepared and a f t e r r e c r y s t a lliz a t io n from methyl alcoh ol-w ater m elted a t l£ 8 -9 ° ( l i t . v a lu e , 1 6 1 ° ) .^ The 2 ,i*-dinitrophenylhydrazone was . o prepared and a f t e r r e c r y s t a lliz a t io n from methyl a lc o h o l m elted a t 11*8 . A nal. C a lc 'd . fo r C13H14N404 : Found: C, £1.7; H, £ .0 ; N, 2 0 .1 . C, £ 1 .7 ; H, £ .2 8 ; N, 2 0 .1 8 . Preparation o f l-chloro-2-m eth yl-3-pen tan on e from d ieth ylk eton e The procedure was analogous to th at described by Colonge. 2 li T hirty-tw o grams o f hydrogen ch lorid e was passed in to 75 m l. o f 36# form alin in a 300 m l. pressure b o t t l e . To t h is m ixture there was 9 added 58 g . (O.7 6 mole) o f d ie th y l k eton e, and the b o t tle was sealed and heated a t 65° fo r two hours. A fter c o o lin g , the upper la y e r was sep a rated , d ried over magnesium s u lf a t e , and d i s t i l l e d , y ie ld in g 13 g . (15$) o f l-chloro-2-m eth yl-3-p en tan on e b o ilin g a t h5 - 52 ° a t li mm,, 25 1.U 355. I t s 2 ,U-dinitrophenylhydrazone m elted a t 87 0 and a mixed m eltin g p o in t w ith the 2,U-dinitrophenylhydrazone of l-c h lo r o -2 -m e th y l3-pentanone prepared from propionyl c h lo r id e , cyclopropane and aluminum ch lo rid e m elted a t 8 9 °. The 2,U -dinitrophenylhydrazones m elted w ith o decom position, then r e - s o l i d if ie d and re-m elted a t about 130 . 2 -M eth yl-l-p en ten e-3-on e was prepared by dehydrohalogenation o f au th en tic l-ch loro-2-m eth yl-3-p en tan on e as described above. b o ile d a t 38° a t 28 mm., n f f 1.U261. The product The 2 ,it-dinitrophenylhydrazone m elted a t lh 7 -8 ° and a mixed m eltin g p o in t w ith the sample p rev io u sly prepared showed no d ep ressio n . The in fra red sp ectra o f both samples o f the unsaturated ketones were id e n t ic a l. Hydrogenation o f 2 -m eth yl-l-p en ten e-3-one F iv e grams (0 .0 5 mole) o f 2-m eth yl-l-p en ten e-3-on e (prepared from the chloroketone r e s u ltin g from the r e a c tio n o f propionyl ch lorid e and cyclopropane) was reduced w ith hydrogen (50 p . s . i . ) u sin g Raney n ic k e l as the c a t a l y s t . In t h ir t y m inu tes, 0 .0 5 mole o f hydrogen was absorbed and th ere was no fu r th e r uptake o f hydrogen. The s o lu tio n was f il t e r e d and d i s t i l l e d , y ie ld in g 3 g . o f e th y l isop rop yl k eton e, b .p . 110-112°, o 27 2 ,h-dinitrophenylhydrazone, m .p. I l l 0 ( l i t v a lu e , 111-113 ) , semi­ carbazone, m.p. 9li° ( l i t . v a lu e , 9 5 ° ) .^ 10 Dehydrohalogenation o f 6-c h loro-3 -hexanone In a $00 m l. three-necked f la s k f i t t e d with a m etal Hershberg s tir r e r , 18 r e f lu x condenser and a d d itio n funnel th ere was p laced 200 m l. o f 10$ sodium hydroxide. T hirty-one grams (0 .2 3 mole) o f 6 -ch lo r o - 3-hexanone (from the r e a c tio n o f propionyl ch lorid e w ith cyclopropane) was added and the s o lu tio n was reflu x ed w ith vigorou s s t ir r in g fo r f i f t e e n m in u tes. A fter d i s t i l l a t i o n , the upper la y e r o f the d i s t i l l a t e was separated and the water la y e r extra cted with e th e r . The combined organic la y e r s were d ried over calcium ch lorid e and then d i s t i l l e d . There was obtained 17 g . (68$) o f e th y l cyclopropyl k etone, b .p . 1*8-$1° a t 3$ mm., i f f l.li2 2 9 ( l i t . v a lu e , b .p . 130 - 132 ° , n£° 1.1*281*, 1.1*298) , 2 0 ’ 28 The 2 ,U-dinitrophenyll$rdrazone m elted a t 162° ( l i t . v a lu e s , 160.1*°, X 70°).19' 28 The R eaction o f Iso b u ty ryl Chloride with Cyclopropane The procedure was e s s e n t ia lly the same as th a t d escribed in d e t a il fo r the r ea c tio n o f propionyl ch lo rid e w ith cyclopropane. From 23$ g . (2 .2 2 m oles) o f iso b u ty r y l c h lo r id e , 29$ g . (2 .2 2 m oles) o f aluminum ch lo rid e and 99 g . (2 .3 3 m oles) o f cyclopropane in 900 m l. o f chloroform th ere was obtained 2$0 g. (77$) o f a mixture o f chloroketones b o ilin g from $3-60° a t 3 mm. The chloroketones were d i s t i l l e d through an e f f i c i e n t column and 113 g . (3^$) o f l-c h lo r o -2 ,l*-dim ethyl-3-pentanone, o 2$ b .p . 1*1 a t 3 mm., n^ 1.1*332-1.1*31*0, was obtained. A nal. C alc*d. f o r C7H130C1: Found: C l, 2 2 .9 , 2 3 .0 . C l, 2 3 .9 . 11 There was a ls o obtained 60 g. (18$) o f 2 -m eth yl- 6 -c h lo r o - 3 -hexanone, b .p . 51*° a t 3 mm., nj^* I .I 4382 . A nal. C a lc 'd . fo r C7 H130C1: Founds C l, 2 3 .9 . C l, 2 3 .3 , 2 3 .5 . An attem pted p reparation o f the 2 ,h-dinitrophenylhydrazone o f l-ch lo ro -2 ,li-d im eth y l-3 -p en tan on e was u n su c c e ssfu l. The 2 ,U -d in itr o - phenylhydrazone o f 2 -m ethyl- 6-c h lo r o - 3 -hexanone was prepared and a fte r r e c r y s t a lliz a t io n from methyl a lc o h o l, m elted a t 10 l;- 5 O. A nal. C a lc'd . fo r C13 H17N4 0 4C1: Found: C, 147.59; H, C, 1*7.5; H, 5 .2 ; N, 1 7 .0 ; C l, 1 0 .8 . N, 16.35; C l, 1 0 .1 1 . Dehydrohalogenation o f 1 -c h lo r o -2 .h-dime thyl-3-pentanone In a 500 m l. three-necked f la s k f i t t e d w ith a r e flu x condenser and a Hershberg s t i r r e r , k9 g . ( 0 .3 3 1 mole) o f l-C h lo ro -2 ,h -d im eth y l-3 pentanone was reflu xed w ith 200 m l. o f 25$ sodium bicarbonate w ith vigorous s t ir r in g fo r two hours. The so lu tio n was co o led , the upper la y e r separated and the water la y e r extracted w ith e th e r . organic la y e r s were dried over potassium carbonate. The combined A fter removal of the s o lv e n t, there was obtained 27 g . (82$) of 2 ,h -d im eth y l-l-p en ten e3 -o n e, b .p . 52 o 25 o a t 39 mm., n^ 1 . 142I48- I .I 42I42 ( l i t . v a lu e , b .p . 55 a t 60 mm.)29 and 5 g . o f recovered 1 -c hlor o -2 ,Ii-d im eth y l-l-p en ten e-3 -o n e. The p-nitrophenylhydrazone melted a t 89-90° ( l i t . v a lu e , 8 9 °)29 and the semicarbazone melted a t 9it-95° ( l i t . v a lu e, 8 9 .5 -9 0 °) , 29 The 2 , 14-dinitrophenylhydrazone was prepared and a f te r r e c r y s t a lliz a t io n from methyl a lc o h o l m elted a t 1 0 6 -7 °. Elemental a n a ly sis checked fo r 12 th e dinitrophenylhydrazone p lu s one m olecule o f w ater. A n al. C a lc‘d . fo r C13H16N406 s Founds C, 5 0 .2l*; H, 5 .8 0 ; N, 18.01*. C, 1*9.87, h9.9h} H, 5 .6 9 , 5.1*0; N, 1 7 .7 8 , 1 7 .9 1 . Hydrogenation o f 2 . l*-dime t h yl-1-p en ten e-3 -one Eleven grams (0 .1 mole) of 2 ,l*-dim ethyl-l-pentene-3-one was reduced ■with hydrogen (50 p . s . i . ) u sin g Raney n ic k e l as the c a t a ly s t . In t h ir t y m inutes 0 .1 mole o f hydrogen was absorbed and there was no fu rth er up­ take o f hydrogen. The s o lu tio n was f il t e r e d and there was d i s t i l l e d 7 .5 g . o f d iiso p ro p y l k eto n e, b .p . 63-1*° a t 80 mm., nj^ 1 .3 9 6 5 , n^° 1 .3 9 9 0 , ( l i t . v a lu e , b .p . 12l*-5°, 1.1*001).3 The 2 ,l* -d in itro - phenylhydrazone m elted a t 9l*-5° ( l i t . v a lu e , 9l*-98°).2^ Dehydrohalogenation o f 6-chloro-2-m ethyl-3-hexanone To a 500 m l. three-necked f la s k f i t t e d w ith a r e flu x condenser and m etal Ifershberg s t i r r e r , Tft 25 g . (0 .1 7 mole) o f 6 -ch loro-2-m eth yl-3- hexanone (from iso b u ty r y l ch lorid e and cyclopropane) was added to 100 m l. o f 10# sodium Iiydroxide. s t ir r in g f o r one hour. The s o lu tio n was reflu xed w ith vigorous The s o lu tio n was co o led , the upper la y e r separated and the water la y e r ex tra cte d w ith e th e r . were dried over potassium carbonate. The combined organic la y e r s A fter the so lv e n t was removed, 16 g . (81*#) o f iso p ro p y l cyclopropyl ketone was ob tain ed , b .p . 61*° a t 1*0 mm., 1.1*263, ( l i t . v a lu e , b .p . 11*1°, n20 1.1*290-1.1*299) . 20,3° The 2 ,l*-dinitrophenylhydrazone was prepared and a f t e r the f i r s t r e c r y s ta l­ l i z a t i o n from methyl a lc o h o l melted a t 17l*-175°. A fter the second and 13 th ir d r e c r y s t a lliz a t io n i t melted a t l61*-5°, ( l i t . v a lu e , 188°) A nal. C a lc 'd . fo r C13H16N404 : Founds C, $ 3. $; H, 5 .5 ; N, 1 9 .2 . C, 5 3 .£9; H, 5.17; N, 19.21*. The r e a c tio n o f n -b u tyryl ch lo rid e w ith cyclopropane The procedure was e s s e n t ia lly the same as th at d escribed in d e t a il fo r the r e a c tio n o f propionyl ch lo rid e w ith cyclopropane. From 160 g . ( 1 .5 m oles) o f n -b u tyryl c h lo r id e , 190 g . ( 1 .5 moles) o f aluminum ch lo rid e and 77 g . (1 .7 9 m oles) o f cyclopropane in 600 m l. o f chloroform , there was obtained the usual m ixture of ch lorok eton es. A fter the s o l ­ ven t had been removed, 500 m l, o f 20$ sodium bicarbonate was added and th e s o lu tio n reflu x ed w ith vigorous s tir r in g u n t il 17 l i t e r s o f carbon d ioxid e had been given o f f (a s measured by a Wet T est M eter). The s o lu ­ tio n was c o o le d , the upper la y e r separated and the water la y e r ex tra cted w ith e th e r . The combined organic la y e r s were dried over potassium carbonate. A fter removal o f th e s o lv e n t, th ere was obtained by d is ­ t i l l a t i o n through a tw enty p la te column 73 g . (1*1$) o f 2-m ethyl- 1 hexene-3-one, b .p . 1*0° a t 13 mm. or 52° a t 23 mm., n ^ 1.1*303. A nal. C a lc 'd . fo r C7H120: Founds C, 7 5 .0 ; H, 1 0 .7 . C, 7 5 .11; H, 10.1*3. There was a ls o obtained 51 g . (23$) o f l-chloro-l*-heptan one, b .p . 87° 25 a t 11 mm., n^ 1.1*1*08. A n al. C a lc'd . fo r C7H130C1: Found: C l, 2 3 .3 , 23.1*. C l, 2 3 .9 . Hi The o r ig in a l mixture o f chloroketones can be otain ed in 70 -80# y i e l d , b .p . 52-62° a t 3 mm. Even when d i s t i l l e d through a twenty p la te column, however, no sharp sep aration o f the two chloroketones was p o s s ib le . The b o ilin g p o in t and r e fr a c tiv e index showed a stead y r i s e . The 2 ,ii-dinitrophenylhydrazone o f 2-m eth yl-l-h exene-3-on e was prepared and a f t e r r e c r y s t a lliz a t io n from methyl a lco h o l melted a t 1 5 6 -7 ° . A nal. C a lc 'd . fo r Found: C, 53.5; H, 5 .5 ; H, 1 9 .2 . C, 53.2U; H, 5 .5 6 ; N, 1 9 .0 2 . The 2 ,li-dinitrophenylhydrazone o f 1-chloro-li-heptanone was an amorphous s o lid and could n o t be c r y s t a lliz e d . De hydro halo genation o f 1-ch loro -It- hep tanone To a 500 m l. three-necked f la s k f i t t e d w ith a m etal Efershberg s tir r e r , g. 1 fi r e f lu x condenser and an a d d itio n fu n n e l, there was added 28 o f sodium hydroxide and 28 m l. o f w ater. S ix ty -e ig h t grams (O.I46 mole) o f 1-chloro-li-heptanone was added slo w ly to the v ig o ro u sly s tir r e d r e flu x in g s o lu t io n . The mixture was reflu x ed fo r an a d d itio n a l f if t e e n m inutes, then co o le d . The upper la y e r was separated and th e water la y e r ex tra cted w ith e th e r . The combined organic la y e r s were d ried over potassium carbonate. A fte r removal o f so lv e n t, there was d i s t i l l e d 28 g . (5355) o f n-propyl cyclopropyl k eton e, b .p . 63 ° a t 27 mm., nj^ I.li3 0 li-l.li3 0 6 ( l i t . v a lu e , b .p . 1 5 1 °, n*° l.ii 3 2 5 ) .2° A nal. C a lc 'd , f o r C7Hla 0: Founds C, 75.0; H, 1 0 .7 . C, 75.35; H, 1 0 .5 . 15 T he 2 ,1 4 - d in itr o p h e n y lh y d r a z o n e w as p r e p a r e d a n d a f t e r fro m m e th y l a l c o h o l m e lte d a t 1 5 2 ° , Anal. ( lit. re c ry s ta lliz a tio n v a lu e , 1 6 5 ° ) .^ C alc'd. fo r Ci3HieH4°4s c , 5 3 .5 ; H, 5 .5 ; n , 1 9 . 2 . Found! C, 5U .03, 51,.12; H, 5 .5 5 , 5 .3 6 ; N, 1 8 .9 2 . Hydrogenation o f 2-m ethyl-l-he;xene-3-one Ten grains (0 .0 9 mole) o f 2-m ethyl-l-h ex en e-3 -o n e was reduced w ith hydrogen (50 p . s . i . ) u sin g Raney n ic k e l as the c a t a ly s t . In t h ir t y m in u tes, 0 .0 9 mole o f hydrogen was absorbed, and there was no fu rth er uptake o f hydrogen. The s o lu tio n was f il t e r e d and there was d i s t i l l e d 7 g , o f propyl iso p ro p y l k eton e, b .p . 130-135° ( l i t . v a lu e , 135-136°) The semicarbazone m elted a t 118° ( l i t . v a lu e , 119°) Preparation o f n-propylcyclopropyl ketone from cyclopropanecarbopyl chloride*^ N in ety -th ree grams (0 .7 li mole) o f n-propyl bromide (prepared from phosphorus tribrom ide and c .p . n-propyl a lc o h o l) ^ in 1|00 m l. o f anhy­ drous eth er was added slo w ly to 18 g . (0 .7 5 m ole) o f magnesium. A fter the r e a c tio n was complete the s o lu tio n was f il t e r e d through g la ss wool and cooled to 0 ° . F i f t y grams (0 .2 7 mole) o f anhydrous cadmium ch lo rid e was slo w ly added and th e s o lu tio n s tir r e d f o r one hour. To the r e s u ltin g mixture was slow ly added 51 g . ( 0 .5 mole) o f cyclopropanecarbonyl ch lo rid e in 100 m l. o f anhydrous eth er and the so lu tio n was reflu xed fo r fo u r hours. D ilu te (6N) s u lfu r ic a cid was slow ly added to the s o lu tio n u n t il the p r e c ip ita te d is s o lv e d . This r e su lte d in a th r e e -la y e r system . 16 The upper two la y e r s were separated from the lower la y e r and anhydrous potassium carbonate was slow ly added to them. carded. The lower la y e r was d is ­ The potassium carbonate was removed by f i l t r a t i o n , and the s in g le la y e r which remained was dried again over potassium carbonate. A fte r removal o f th e so lv en t there was d i s t i l l e d 26 g . 0x1%) o f n-propyl cyclop rop yl k eton e, b .p . 62° a t 2$ mm., n ^ 1 ,1;299-1 .h 3 0 1 . The 2 ,h-dinitrophenylhydrazone m elted a t lf>2° and the mixed m elting p o in t w ith the 2 ,h-dinitrophenylbydrazone of n-propyl cyclopropyl ketone prepared from 1-chloro-h-heptanone showed no d ep ression . The in frared spectrum was e s s e n t ia lly id e n tic a l w ith th a t o f the n-propyl cyclop rop yl ketone prepared from the chloroheptanone excep t fo r minor shoulders a t $ .18 fA , 8.1*0-8.5>2 fA and a lon ger peak a t 7 .8 8 j a The spectrum was run in carbon te tr a c h lo r id e , carbon d is u lf id e and as the pure liq u id . Preparation o f 2-ethylcyclopentanone A s o lu tio n o f 30 g . (0 .1 6 mole) o f 2-eth y l-2 -ca rb o eth o x y cy clo p en tanon e,^ > 3£ go m l# ethanol and 200 m l. o f 20$ sodium hydroxide was s tir r e d fo r three hours a t room tem perature. S u lfu ric a cid (1 :1 ) was added to the s o lu tio n u n t i l i t was a cid to Congo red paper and the s o lu ­ tio n was then reflu x ed fo r two hours. The mixture was co o led , the upper la y e r separated and the water la y e r extracted w ith e t h e r . organic la y e r s were d ried over magnesium s u lf a t e . The combined A fter removal o f the s o lv e n t , there was d i s t i l l e d 2 .1 g . o f 2-eth ylcyclop en tan one, b .p . 66-67° 2$ a t 21 mm., n^ 1.1*368. The semicarbazone melted a t 181 o ( l i t . v a lu e , 17 o 36 177 ) . The 2 ,l*-dinitrophenylhydrazone m elted a t 153-1*° a f t e r r e ­ c r y s t a lliz a t io n from m etly l a lc o h o l. The mixed m eltin g p o in t w ith the 2 ,U-dinitrophenylhydrazone o f n-propyl cyclop rop yl ketone showed on ly a s lig h t depression b ein g 11*9-151°. The in frared s p e c tr a , however, o f 2-ethylcyclopentanone and n-propyl cyclop rop yl ketone were d i s t i n c t l y d if f e r e n t . R eaction o f a c e t y l ch lo rid e w ith cyclopropane The procedure was e s s e n t ia lly the same as th a t described in d e t a il fo r the r e a c tio n o f propionyl ch lorid e w ith cyclopropane. From 156 g . (2 m oles) o f a c e ty l c h lo r id e , 266 g . (2 m oles) o f aluminum c h lo r id e , 90 g . ( 2 .1 m oles) o f cyclopropane in one l i t e r o f chloroform th ere was obtained th e u su al m ixture o f ch lorok eton es. Upon vacuum d i s t i l l a t i o n th ere was obtained 72 g . ( 30$) o f 5-chloro-2-p en tan on e, b .p . 71-8° a t 22 mm. ■Anal. 1.1*368 ( l i t . value 70-72 a t 20 rara.).^ C a lc 'd . fo r C6HgOCl: Found: C l, 29.1*. C l, 2 8 .3 , 2 8 .9 . The semicarbazone was prepared and a f t e r r e c r y s ta lliz a t io n from methyl a lco h o l-w a ter m elted a t 101*° ( l i t . v a lu e , 9 1 - 2 ° ) .^ The 2 ,i* -d in itr o - phenylhydrazone was prepared and a f te r r e c r y s t a lliz a t io n from methyl a lc o h o l m elted a t 1 2 7 °. A n al. C a lc 'd . f o r C ^ H ^ N ^ d : Found: C, 1*3.9; H, 1*.3; N, 1 8 .6 ; C l, 1 1 .7 . C, l*l*.l6; H, 1*.70; N, 18.36; C l, 1 1 .5 9 . 5-C h loro-2-pentanone was prepared from d. - a c e t y l- T -butyrolactone 18 th e semicarbazone m elted a t 101*° and the 2 ,l*-dinitrophenylhydrazone and 18 m elted a t 1 2 7 °. The mixed m eltin g p o in ts showed no d ep ressio n . Seventy grams o f m a te r ia l, c o lle c t e d from the dry ic e trap in the d i s t i l l a t i o n o f 5-ch loro-2-p en tanon e, was dried over potassium carbonate. One gram o f hydroquinone was added and 58 g , ( 36 #) o f 3-m ethyl-3-butene2-one was d i s t i l l e d , b .p . 1*5-6° a t 98 ram., 1 . 1*229 - 1 . 1*21*2 ( l i t . v a lu e , 0 20 b .p , 1*5-6 a t 100 ram., 1.1*163) .** The compound s t i l l contained a tra ce o f c h lo r in e which was im p ossible to remove without polym erizing th e m a te r ia l. The 2 ,l*-dini t rophenylhydrazone was prepared and a fte r r e c r y s t a lliz a t io n from methyl a lco h o l m elted a t 186-7° ( l i t . v a lu e , o 39 192 ) . The semicarbazone was prepared and a f te r r e c r y s t a lliz a t io n from methyl a lco h o l-w a ter m elted a t 170° ( l i t . v a lu e , 17l*-6°) The d eriva­ t iv e s did n ot con tain c h lo r in e . Preparation o f 3-m ethyl-3-butene-2-one from methyl eth y l ketone The procedure was analogous to th a t used by Landau and Irany. 1*1 F ive m i l l i l i t e r s o f 5 N potassium hydroxide was added to 350 g. (5 m oles) o f m ethyl e th y l ketone con tain in g 30 g . (1 mole) o f para­ formaldehyde and the so lu tio n was s tir r e d fo r two hours a t a temperature between 35 and 1*5°. The s o lu tio n was n eu tra lized w ith a c e tic a cid and the e x ce ss methyl e th y l ketone was removed by d i s t i l l a t i o n . F ive m i l l i - l e t e r s o f 85$ phosphoric a c id , 0 .5 g . o f copper powder and 0 .5 g . o f hydroquinone were added and the resid u e was d i s t i l l e d a t a pot tempera­ ture o f 120-130° in a stream o f n itro g e n . The d i s t i l l a t e was washed tw ice w ith water and dried w ith potassium carbonate. There was obtained 30 g . o f 3-raetb yl-3-b u ten e-2-on e, b .p . 1*8-53° a t 101* mm. The f r a c tio n 19 o b o ilin g a t 52-3 , pA 1.1*183, was used in making d e r iv a tiv e s . The 2,1*- dinitrophenylhydrazone m elted a t 186° and the semicarbazone a t 17U°. The mixed m eltin g p o in ts w ith the corresponding d e r iv a tiv e s of 3-m ethyl3-butene-2-one prepared from a c e ty l ch lorid e and cyclopropane showed no d ep ressio n . Hydrogenation o f 3-m ethyl-3-butene-2-one (from a c e ty l ch loride and cyclopropane) F ive grams (0 .0 6 mole) o f 3-m ethyl-3-butene-2-one was reduced with hydrogen (50 p . s . i . ) u sin g Raney n ic k e l as the c a t a ly s t . In t h ir t y m inutes 0 .0 6 mole o f hydrogen was absorbed and there was no fu rth er uptake o f hydrogen. The s o lu tio n was f il t e r e d and 2 .5 g . o f m ethyl i s o ­ propyl ketone was d i s t i l l e d , b .p . 95-100° ( l i t . v a lu e , 9 3 - ^ ° ) .^ A tra ce o f c h lo r in e was s t i l l p resent in the compound. The 2 ,11-dinitro- phenylhydrazone m elted a t 1 2 0 °, the p-nitrophenylhydrazone m elted a t 27 105 ° ( l i t . v a lu e s , 117° and 107 ° r e s p e c tiv e ly ) . Dehydrohalogenation o f 5-chloro-2-pentanone 18 Seventy-two grams ( 0 .6 mole) o f 5-chloro-2-pentanone (from a c e ty l ch lo rid e and cyclopropane) was added to a so lu tio n o f 36 m l. o f water and 36 g . o f sodium hydroxide. The s o lu tio n was reflu xed fo r f if t e e n m inutes w ith vigorous s t ir r in g and then steam d i s t i l l e d . The upper la y e r o f the d i s t i l l a t e was separated and the water la y e r extracted w ith e th e r . The combined organic e x tr a c ts were dried over potassium carbonate and 36 g . (71%) o f methyl cyclopropyl ketone, b .p . 110-111°, nj^ 1,1*222 20 ( l i t . v a lu e , b .p . 110-112°, l.it2 2 6 ) 18 was d i s t i l l e d . The 2 ,it-d in itr o - phenylhydrazone m elted a t lit7° ( l i t . v a lu e , lit9-50°) The r e a c tio n o f benzoyl chloid.de w ith cyclopropane Benzoyl ch lo rid e (281 g . , 2 m oles) was added to a cooled mixture o f 266 g. (2 m oles) o f aluminum ch lo rid e and 1100 m l. o f chloroform . To the cold s o lu tio n was added 100 g. (2 .3 8 m oles) o f cyclopropane. There was no temperature r i s e on a d d itio n of the cyclopropane, such as occurred w ith the a lip h a tic acid c h lo r id e s . The s o lu tio n was s tir r e d a t room temperature fo r tw enty-seven hours, then poured in to a mixture of 1500 g . o f cracked ic e and 300 m l. o f concentrated hydrochloric a c id . The chloroform so lu tio n was washed once w ith one l i t e r of water and s tir r e d overnight with one l i t e r of 10 % sodium bicarbonate to hydrolyze the unreacted benzoyl c h lo r id e . The chloroform la y e r was sep arated , d ried over calcium c h lo r id e , and the so lv e n t removed in vacuo a t ltO°. There was d i s t i l l e d 232 g . (6h%) o f mixed ch lorok eton es, b .p . 128-150° a t 5 iron. The mixture was r e d is t ill e d through an e f f i c i e n t column and o 2 1) 118 g . (32#) o f >0 -cKLoroisobutyrophenone, b .p . lilt a t it mm., nQ 1 ,5 itl8 -l ,5it25 and 51 g . (lit/0 o f 7 -chloro-n-butyrophenone, b .p . 126 - 129 ° a t 5 nan., 1 . 5U62-1.5it90 ( l i t . v a lu e , b .p . I 3 O-I 330 a t it mm. or 1 3 3 .5 - 135° a t 11 m m .)^ » ^ was ob tained . The 2,it-dinitrophenylhydrazone o f /& -chloroisobutyrophenone was prepared and a fte r r e c r y s t a lliz a t io n from methyl a lco h o l melted a t lit 3° . A n al. C a lc 'd . fo r C16 H15N404 : Found: C, 52.9; H, it .lj N, I5 .it; C l, 9 .7 . C, 5it.it8; H, it.53j N, lit.1 6 ; C l, 7 .2 . 21 For a comment on the poor agreement in the a n a ly s is , see the bottom o f page 7 . Preparation o f f t -chloroisobutyrophenone from propiophenone T h ir ty -s ix grams o f hydrogen ch lorid e 30% form alin in was d isso lv ed in 80 m l, o f a 300 m l. pressure b o t t le . N in ety -eig h t grams (0 .7 3 mole) o f propiophenone was added, the b o t t le was sealed and heated on a steam bath fo r th ree hours, w h ile s tir r e d w ith a magnetic s t ir r e r . The b o t t le was c o o le d , the upper la y e r separated and th e water la y e r ex tra cted w ith e th e r . carbonate. The organic la y e r s were dried over potassium A fter removal o f the so lv en t and unreacted propiophenone, 51 g . (iiO$) o f ft -chloroisobutyrophenone was obtained, b .p , 10h-107° a t 3 mm., n ^ 1.536U -1.5372. The poor agreement o f the r e fr a c tiv e in d ic e s i s b elie v ed due to the incom plete sep aration o f the two isom ers formed from the r e a c tio n o f benzoyl ch lo rid e and cyclopropane. Dehydro halo genat ion o f f t -chloroisobutyrophenone F i f t y - f i v e grams (0 .3 mole) o f ft -chloroisobutyrophenone and 200 m l. o f 20% sodium bicarbonate were reflu x ed w ith vigorous s t ir r in g fo r two hours. The s o lu tio n was co o le d , the tipper la y e r separated and th e water la y e r ex tra cted w ith e th e r . over potassium carbonate. Theorganic la y e r s were dried A fter removal o f the s o lv e n t 2h g . (60$) of ot-m ethylacrylophenone was d i s t i l l e d , b .p , 71-2 o 25 a t 2 mm., n^ 1.5369- 1.5377 ( l i t . v a lu e , b .p . 60° a t 3 mm., n^0 1 .5 3 5 U ).^ Cfc -Me thylacrylophenone was prepared from the two chloroketone p rep arations d escribed above. The phenylhydrazones m elted a t 121-2° and the mixed m eltin g p o in t showed no depression ( l i t . v a lu e , 119-20°) Hydrogenation o f Ql -methylacrylophenone F ifte e n grams ( 0 .1 mole) o f €fc-methylacrylophenone was reduced w ith hydrogen (50 p . s . i . ) u sin g Raney n ic k e l as the c a t a ly s t . In one hour 0 .1 mole o f hydrogen was absorbed and there was no fu rth er uptake o f hydrogen. The s o lu tio n was f il t e r e d and 13 g . o f isobutyrophenone, b .p . 76-79° a t 3 mm., n ^ 1.5185 ( l i t . v a lu e, b .p . 95-8° a t 10 mm., n ^ 27 1.5196) was ob tain ed . Both samples o f the unsaturated ketone were reduced to iso b u ty ro ­ phenone. The 2,i*-dinitrophenylhydrazones o f both m elted a t 1 5 7 -8 °, and the mixed m eltin g p o in t showed no depression ( l i t . v a lu e , 1 6 3 °). I 7 Dehydrohalogenation o f *Y -chloro-n-butyrophenone F ifty -o n e grams (0 .2 8 mole) o f y -chloro-n-butyrophenone and 200 m l. o f 10# sodium hydroxide were reflu x ed with vigorous s t ir r in g fo r 75 m in u tes. The s o lu tio n was co o led , the upper la y e r separated and the water la y e r ex tra cted w ith e th e r . d ried over potassium carbonate. The combined organic la y e r s were A fter removal o f the s o lv e n t, there was obtained 25 g . (61#) o f phenyl cyclopropyl ketone, b .p . 88 - 90 ° a t 3 mm., n£5 1 .5 5 ll* -1 .5 5 l6 ( l i t . v a lu e , b .p . 117° a t 1 0.5 mm., n ^ 1 .5 5 lit, ng0 1 . 5 5 6 7 ) The 2,U-dinitrophenylhydrazone was prepared and a fte r r e c r y s t a lla t io n from methyl a lcoh ol m elted a t 1^9 - 50 ° ( l i t . v a lu e , „ ^.o „ o . I48 . 2*9 23 The semicarbazone was prepared and a fte r r e c r y s t a lliz a t io n from methyl a lco h o l-w a ter m elted a t 180° ( l i t . v a lu e , 1 8 2 - 3 ° ) .^ R eaction o f cyclopropanecarbonyl ch lorid e w ith cyclopropane The procedure was e s s e n t ia lly the same as th at d escribed in d e t a il fo r th e r e a c tio n o f propionyl ch lorid e w ith cyclopropane. From 116 g , ( l . l l m oles) o f cyclopropanecarbonyl c h lo r id e , llt8 g . (1 .1 1 m oles) o f aluminum ch lo rid e and 55 g . (1 .3 1 moles) o f cyclopropane in 500 m l. o f chloroform , there was obtained the usual mixture o f ch lorok etones. A fter the s o lv e n t had been removed, 1±00 m l. o f 20# sodium bicarbonate and te n grams o f hydroquinone were added and the s o lu tio n was reflu x ed w ith vigorous s t ir r in g fo r 1*5 m inutes. During t h is time there was given o f f f i f t e e n l i t e r s o f carbon d ioxid e (as measured by a Wet T est M eter). The s o lu tio n was c o o le d , the upper la y er separated and the water la y er ex tra cte d w ith e th e r . potassium carbonate. The combined organic la y e r s were dried over A fter removal o f the so lv e n t there was obtained by d i s t i l l a t i o n through a te n p la te column 36 g . (3°$) o f cyclopropyl isop rop en yl k eton e, b .p . 57-58° a t 21 mm., nj^ l.i» 6 l8 . Anal. C a lc 'd . fo r C7Hlo0: Found: C, 7 6 .U; H, 9 .1 . C, 7 k M ; H, 9 .1 9 . This compound had s e t to a white polymer before b ein g analyzed. The 2 ,U -dinitrophenylhydrazone was prepared and r e c r y s ta lliz e d from methyl a lc o h o l. The b rig h t red c r y s ta ls turned from red to brown a t a temperature from 150-170° and decomposed in to a black liq u id from 2k 170-175 . A elem ental a n a ly s is agreed moderately w e ll fo r the phenyl- hydrazone p lu s one m olecule o f w ater. A n a l. C a lc'd . f o r C13H16N406 : Found* C, 50.63; H, 5 .1 9 ; N, 1 8 .1 6 . C, 119.1*9, 1*9.55; H, U .96, 1*.90; N, 1 7 .8 1 , 1 8 .0 0 . There was a lso obtained 20 g , o f a chloroketone, b .p . 66-76° a t 10 ran., n ^ 1.1*592. I n a l. C a lc 'd . f o r C7Hllt0C l: Found: C l, 2i*.2. C l, 2 1 .2 , 2 1 .3 . The 2 ,U-dinitrophenylhydrazone was prepared and a f t e r r e c r y s ta lliz a t io n from m ethyl a lc o h o l m elted a t 12 i*-125 ° . A nal. C a lc'd . fo r C13H16N404C1: Found: C, 1*7.8; H, 1*.6; N, 1 7 .1 ; C l, 1 0 .9 . C, 1*8.00; H, l*.8l; N, 16.11*; C l, 1 0 .0 7 . Hydrogenation o f cyclopropyl isopropenyl ketone Fourteen grams (0 .1 2 7 mole) o f cyclopropyl isopropenyl ketone was reduced w ith hydrogen (50 p . s . i . ) w ith Raney n ic k e l as the c a t a ly s t . In one hour there was absorbed 0 .1 3 mole o f hydrogen and there was no fu rth er uptake o f hydrogen. The s o lu tio n was f ilt e r e d and there was d i s t i l l e d 11 g . o f cyclop rop yl iso p ro p y l k eton e, b .p . 50-51° a t 21 mm., 1.1*273. The in fra red spectrum was compared with th a t o f authentic iso p ro p y l cyclop rop yl ketone p rev io u sly prepared and th ey were found to be id e n t i c a l . 25 Dehydrohalogenation o f the chloroketone from cyclopropanecarbonyl ch lo rid e and cyclopropane N ineteen grama o f the chloroketone, b .p . 66-76° a t 10 mm. was added to $0 m l. o f 20$ sodium hydroxide. vigorous s t ir r in g f o r 30 m in utes. w ith potassium carbonate. la y e r ex tra cte d w ith e th e r . potassium carb on ate. The s o lu tio n was reflu x ed with The s o lu tio n was cooled and satu rated The upper la y e r was separated and the water The combined organic la y e r s were dried over A fter removal o f the so lv e n t there was d i s t i l l e d 3 g . o f a y ello w ketone b .p . 60-70° a t 20 mm. I t s in fra red spectrum showed th e presence o f a double bond. S ix grams o f a y ello w ketone o b .p . 85-92 a t 20 mm, was a lso d i s t i l l e d . I t s in frared spectrum showed the presence o f a hydroxyl group. N either fr a c tio n was in v e stig a te d fu r th e r . R eaction o f n-propylcyclopropyl ketone w ith hydrogen ch lo rid e in the presence o f aluminum ch lorid e In a 500 m l. three-necked f la s k , f i t t e d with a s t i r r e r , thermometer, and gas i n l e t tube there was placed 51 g . (0 .3 8 mole) o f aluminum ch lo rid e in 100 m l. o f chloroform . The m ixture was cooled in an ic e bath to 0 ° and k3 g . ( 0 .3 8 mole) o f n-propyl cyclopropyl ketone was added. A n hydrous hydrogen ch lo rid e was then passed through the s o lu tio n a t 0° fo r 105 m in u tes. Then the solution- was slow ly poured in to a mix­ ture o f 100 m l. o f concentrated hydrochloric acid and 300 g . o f cracked ic e . The chloroform la y e r was separated and washed once with w ater, once w ith 10$ sodium bicarbonate and again w ith water and dried over 26 potassium carbonate. There was d i s t i l l e d y~> g . (81$) o f propyl c y c lo - propyl k eto n e, b .p . 60 o 2*5 a t 22 mm., n^ 1.1*302. The in frared spectrum was id e n t ic a l w ith the n-propyl cyclopropyl ketone used a s the s ta r tin g m a te r ia l. There was no evidence o f any other r e a c tio n product. The r e a c tio n o f propionyl ch lorid e w ith cyclopropane in the presence o f f e r r ic ch lo rid e Propionyl ch lo rid e (1+7 g . , 0 .5 mole) was added to a cooled mixture o f 81 g . ( 0 .5 mole) o f f e r r ic ch lorid e in 300 m l. o f chloroform . Cyclo­ propane (21 g . , 0 .5 mole) was added and the s o lu tio n was s tir r e d fo r e ig h t hours in an ic e b a th . The s o lu tio n was poured in to a m ixture of 100 m l. o f concentrated hydrochloric acid and 300 g . o f cracked i c e . The chloroform la y e r was washed once w ith 6 N hydrochloric a c id , once w ith w ater, once with 10$ sodium bicarbonate s o lu tio n and again with w ater. The so lu tio n was dried over calcium ch lo rid e and the so lv en t was removed in vacuo a t 1*0°. There was obtained 20 g. (30$) o f l-c h lo r o - 2 - m ethyl-3-pen tanone, b .p . 52-56 o 25 a t 5 mm., nD 1.1+322-1.1+31+9, alm ost a l l o f which b o ile d a t $6° a t 5 mm., n ^ 1.1+31*9. The 2 ,i+-dinitrophenyl- hydraaone m elted a t 87-8° and a mixed m eltin g p o in t w ith an au thentic specimen showed no d ep ressio n . R eaction o f propionyl ch lorid e w ith cyclopropane in nitromethane Propionyl ch lo rid e (1+6 g . , 0 .5 mole) was added to a cooled s o lu tio n o f 66 g . ( 0 .5 mole) o f aluminum ch lo rid e in 300 m l. o f nitrom ethane. The mixture was s tir r e d fo r one l» u r but the a cid chloride-aluminum 27 ch lo r id e complex d id n ot go in to s o lu tio n . Cyclopropane (21* g . , 0.57 mole) was added and the s o lu tio n was s tir r e d ten hours in an ic e b a th . The s o lu tio n was slo w ly poured in to a mixture of 100 m l. concentrated hydrochloric a cid and 300 g. o f cracked i c e . The s o lu tio n was washed once w ith w ater, once w ith 10$ sodium bicarbonate and again w ith w ater. The nitromethane s o lu tio n was dried over calcium c h lo r id e . The so lv en t was removed in vacuo a t 1*0° and 9 g . o f m aterial b .p . 52-67° a t 5 mm. was c o lle c t e d . The m a teria l was not fu rth er in v e s tig a te d . The r e a c tio n o f phosgene w ith cyclopropane Phosgene (73 g . , 0.1*7 mole) was d isso lv e d in 100 m l. o f chloroform . This s o lu tio n was added to a cooled s o lu tio n o f 200 g . (1 .5 m oles) of aluminum ch lo rid e in 500 m l. o f chloroform . The mixture was s tir r e d fo r 30 minutes but most o f the aluminum ch lo rid e did not go in to s o lu tio n . Cyclopropane (103 g . , 2.1*5 m oles) was added over a period o f two hours and the s o lu tio n was s tir r e d fo r two more hours. The so lu tio n was poured in to a m ixture o f 200 m l. o f concentrated hydrochloric a cid and 1000 g. o f cracked i c e , then s tir r e d fo r one hour. The chloroform la y er was washed w ith w ater, 10$ sodium b icarb on ate, and again w ith w ater. A fte r drying over potassium carbonate, the so lv en t was removed in vacuo a t 1*0°. There was d i s t i l l e d , w ith some decom position, 9 g . o f m aterial b o ilin g from 85° a t 1* mm. to 125° a t 10 mm., and th ere was considerable resid u e in the p o t. The m a teria l was not fu rth er in v e s tig a te d . 28 A nalyses The method o f Umhoefer f i and V -ch lo ro k eto n es. 23 was used fo r the ch lo rin e a n a ly sis o f About 0.25-0.1*0 g . o f or T -chloroketone was placed in a 250 m l. fla t-b ottom ed f la s k , follow ed by 25 m l. o f i s o ­ propyl a lc o h o l. Two grams o f sodium cut in to four or f iv e p ie c e s was added and the s o lu t io n reflu xed one to two hours. The ex cess sodium was decomposed by c a u tio u s ly adding water through the condenser. S ix ty m i l l i l i t e r s o f water was added, the s o lu tio n co o led , and n eu tra lized to Congo red paper w ith 6N n it r ic a c id . The ch lorid e ion was t it r a t e d by the standard Volhard method. A ll o th er an alyses were performed by Clark M icroan alytical Laboratory, Urbana, I l l i n o i s . M elting P oin ts M elting p o in ts were taken in a c a p illa r y in a e f f i c i e n t l y s tir r e d o i l b ath. The thermometer was c a lib ra te d a g a in st a Bureau o f Standards thermometer. 29 DISCUSSION The r e a c tio n o f a cid c h lo rid es w ith cyclopropane in the presence o f aluminum ch lo rid e was in v e stig a te d to determine i f t h is r e a c tio n would give a convenient method fo r preparing T -ch loroketon es and th ereb y , cyclop rop yl k eto n es. Cyclopropane was found to r ea ct e a s ily w ith acid c h lo r id e s , even a t temperatures as low as a -1*0°, to give a 60-80$ y ie ld o f a mixture o f two ch lo ro k eto n es. The acid ch lo rid e and aluminum ch lo rid e were used in a 1 :1 mole r a tio in a coloroform s o lu tio n , and a s lig h t ex cess o f c y c lo ­ propane was passed in to the s o lu t io n , keeping the temperature below 2 0 °. The r e a c tio n was exothermic excep t in the case o f benzoyl c h lo r id e . I f t e r an hour, the product was worked up by the usual method fo r F r ie d e lC rafts r e a c tio n s . In stea d o f o n ly a s in g le product ( i . e . , the expected -ch lo ro k eto n e) , a mixture o f chloroketones was obtain ed . I . Proof o f Structure o f the Lower B o ilin g Chloroketones a . Propionyl Chloride and Cyclopropane The chloroketones r e s u ltin g from the rea ctio n o f propionyl ch lo rid e w ith cyclopropane were separated by fr a c tio n a l d i s t i l l a t i o n . Two main fr a c tio n s were o b ta in ed , and ch lo rin e a n a ly sis in d ica ted th a t th ey were iso m ers. The gen eral scheme fo llo w ed fo r detennining the stru ctu re of the low er b o ilin g fr a c tio n was as fo llo w s: 30 ^.CH2 CH2 I ^CH 3 fl + CH3-CH2-C-C1 g CH; CH3-CH3-C-Ck CH,2 \ \ Ho _ ,CH2C1 ch3- ch2-'' CH3-CH2-C-CH2-CH2 + H-C-H t + ■•ch3 fE l J OB3 CHa-CH2-C-CH . h ^CH3 in unequivocal s y n th e sis of l-chloro-2-m eth yl-3-pentanon e was made from d ie th y l k eton e, formaldehyde and hydrochloric acid and the 2 ,it-d initrophenylhydrazone was prepared. The m elting p o in t was the same as th a t fo r th e 2,l*-dinitrophenylhydrazone prepared from the lower b o ilin g chloroketone and the mixed m eltin g p o in t showed no d ep ression . 2-Methyl- l-p en ten e-3 -o n e was prepared from both samples o f /$ -ch lorok eton e. The semicarbazone o f 2-m ethyl-l-p en ten e-3 -o n e (from the f i -chloroketone sy n th esized from propionyl ch lorid e and cyclopropane) m elted very c lo se to the reported m eltin g p o in t. The 2,i4-dinitrophenylhydrazones of both samples o f 2-m eth yl-l-p en ten e~3-one m elted a t the same temperature and a mixed m eltin g p o in t showed no d ep ressio n . Furthermore the in frared sp ectra o f the two samples o f the unsaturated ketone were id e n t ic a l. k sample o f 2-m ethyl-l-p e n te n e-3 -o n e (from the /3 -chloroketone synth esized from p ropionyl ch lo rid e and cyclopropane) was reduced to e th y l isop rop yl k eton e. The 2 ,]+-dinitrophenylhydrazone and semicarbazone gave the expected m eltin g p o in t s . 31 b . Iso b u ty r y l Chloride and Cyclopropane The lower b o ilin g chloroketone was dehydrohalogenated to the cor­ responding unsaturated k etone. The p-nitrophenylhydrazone and semi­ carbazone were prepared and t h e ir m eltin g p o in ts checked w ith those reported fo r 2 ,l4 -d im eth y l-l-p en ten e-3 -o n e. The unsaturated ketone was reduced to d iiso p ro p y l ketone and the 2,h-dinitrophenylhydrazone was prepared. I t m elted a t the reported v a lu e. c . A cety l Chloride and Cyclopropane While t h is fr a c tio n always contained a trace of c lilo r in e , i t con­ s is t e d m ainly o f the unsaturated ketone formed by the spontaneous dehydrohalogenation o f the /3 -ch lo ro k eto n e. 2-M ethyl-3-butene-2-one was prepared from methyl e th y l ketone, formaldehyde and potassium hydroxide and the 2 ,!t-dinitrophenylhydrazone and semicarbazone were prepared. The m eltin g p o in ts o f the 2 ,h-dinitrophenylhydrazone and semicarbazone o f th e unsaturated ketone (from a c e ty l ch lorid e and c y c lo ­ propane) m elted on ly s li g h t l y lower than the corresponding d e r iv a tiv e s from 3-m ethyl-3-butene-2-one and the mixed m elting p o in t showed no d ep ressio n . The unsaturated ketone (from a c e ty l ch lo rid e and c y c lo ­ propane) was reduced to methyl isop rop yl ketone. The m elting p o in ts o f the 2 ,h-dinitrophenylhydrazone and p-nitrophenylhydrazone agreed w ell w ith reported v a lu e s . d . Benzoyl Chloride and Cyclopropane The lower b o ilin g chloroketone was de hydro halo gena ted to the co rres­ ponding unsaturated k eton e. ^-C hloroisobutyrophenone (made from 32 propiophenone, formaldehyde and hydrochloric a cid ) was dehydrohalogenated to dr -methylacrylophenone and the phenylhydrazone prepared. The m elting p o in t o f t h i s phenylhydrazone and the phenylhydrazone prepared from the unsaturated ketone (from the lower b o ilin g chloroketone) m elted a t the reported tem perature. A mixed m eltin g p oin t showed no d ep ression . Both samples o f oL -m ethylacrylophenone were reduced to isobutyrophenone. The 2 ,U -dinitrophenylhydrazones o f both m elted s l i g h t l y lower than reported v a lu e s , but a mixed m eltin g p o in t showed no d ep ression . e * n-Butyryl Chloride and Cyclopropane The sep aration o f the two chloroketones could not be made by d is ­ t illa t io n . Therefore the /& -chloroketone was s e le c t iv e ly dehydrohalo- genated by r e flu x in g w ith a sodium bicarbonate s o lu tio n . Tliis perm itted an easy sep aration o f th e unsaturated ketone and the other chloroketone by fr a c tio n a l d i s t i l l a t i o n . This unsaturated ketone was shown to be 2 -m eth yl-l-h exen e-3-on e by reduction to propyl isop rop yl ketonej the m eltin g p o in t o f i t s semicarbazone agreed w ell w ith the reported v a lu e . f . Cyclopropanecarbonyl Chloride and Cyclopropane The two chloroketones could not be separated by d i s t i l l a t i o n . They were th erefo re reflu x ed w ith a sodium bicarbonate s o lu tio n and the / t -ch loroketon e s e le c t i v e l y dehydrohalogenated. The low er b o ilin g unsaturated ketone was shown to be isopropenyl cyclopropyl ketone by red u ction to iso p ro p y l cyclopropyl ketone. I t s in frared spectrum was id e n t ic a l w ith the spectrum o f a sample of isopropyl cyclopropyl ketone prepare d from 6 - c h loro-2-m ethyl- 3 - hexanone. 33 Im summary, th en , the proof o f stru ctu re o f the jS -ch loroketon es s ta r te d not w ith th e u n stab le chloroketone but w ith the corresponding unsaturated k eto n e. Infrared spectra and m elting p o in ts and mixed m eltin g p o in ts o f d e r iv a tiv e s were used to prove th e id e n t it y o f the unsaturated k eto n e s. The unsaturated ketones were a ls o reduced to i s o ­ propyl ketones and the m eltin g p o in ts o f d e r iv a tiv e s confirmed th e ir id e n tity . The foregoin g proof o f stru ctu re shows th a t one course o f the re a c tio n between acid ch lo rid es and cyclopropane i s as shown: R-C-Cl .8 + In g e n e r a l, approxim ately tw o-th ird s o f the rea ctio n takes t h is p ath . This method could be o f sy n th e tic value f o r the preparation o f most isop rop en yl k eto n es, sin ce the ^ -c h lo r o k e to n e s are so r e a d ily dehydro­ halo genated. R eflu xin g the m ixture o f products w ith a sodium bicarbonate s o lu tio n transform s th e fi -ch loroketon es to unsaturated k eton es, but does not a f f e c t the oth er r e a ctio n p roducts. The unsaturated ketones b o il much lower than the other r e a c tio n p rod ucts, and can e a s ily be separated by f r a c tio n a l d i s t i l l a t i o n . This rea ctio n p rovides the only convenient method f o r preparing n-propyl isopropenyl ketone because in t h is case the usual method would give a mixture o f unsaturated k eto n es. These ketones would be very d i f f i c u l t to sep a ra te. 3k i ch3- ch2- ch2 -CH2-CH3 + H-C-H ffil NaHCO- CHa-CHa-C^-C-COHa 6 h3 c h3-c h2-c -$ -c h3-c h3 Kh2 I I . Proof o f Structure fo r the Higher B o ilin g Chloroketones From Acid CtSorid.es and Cyclopropane ' """ These chloroketones proved to be the a n tic ip a te d k e to n e s. -chloropropyl Upon de hydrohalo gen ation , th ey gave cyclopropyl k eto n es. A ll o f the cyclop rop yl ketones thus obtained were p rev io u sly known and th e ir i d e n t i t y was e sta b lish e d by d e r iv a tiv e s and by t h e ir infrared sp e ctra . A r e p r e sen ta tiv e example i s the proof o f stru ctu re o f l-chloro-U -heptanone (from n -b u tyryl ch lo rid e and cyclopropane). CH3-C H2-C Ha-C-C H2-C Ha-C HaCI 1 -Chloro-1|-hep tanone was dehydrohalogenated to y ie ld propyl cyclopropyl k eton e. The in fra r ed spectrum had the c h a r a c te r is tic carbon-hydrogen bands o f cyclop rop yl ketones bond). 30 and had no band a t 6 .0 -6 .5 JA (double The ketone and 2 ,li-dinitrophenylhydrazone had the co rrect elem ental a n a ly s is . Propyl cyclopropyl ketone was a lso prepared from cyclopropanecarbonyl ch lo rid e and d i-n -p rop yl cadmium. y? I t s 2,U -dinitrophenylhydrazone m elted a t the same temperature a s the 2 ,U -dinitrophenylhydrazone o f propyl cyclopropyl ketone prepared from l-ch lo ro -U -h ep ta n o n e. A mixed m eltin g p o in t showed no d ep ressio n . The in fra red sp ectra o f the two samples were e s s e n t ia lly id e n t ic a l. Since the dehydrohalogenation o f 1-chloro-h-heptanone could give e it h e r a three-raembered or a five-membered r in g , CH3-CH2-9H CH.*— CH CH2 an au th en tic sample o f 2-ethylcyclopentanone was prepared. The in fr a ­ red spectrum was compared w ith the spectrum o f propyl cyclop rop yl ketone prepared from 1-ch loro-ii-h ep tan on e, and i t was found to be d is t in c t l y d iff e r e n t (se e pages 3 6 , 37) . The re a c tio n o f a c id c h lo rid es w ith cyclopropane might be o f value f o r preparing sm all amounts o f ? -chloropropyl ketones and cyclopropyl k eto n es, but the low y ie ld lim it s i t s a p p lic a tio n . I I I . Notes on Experimental Procedure a . Dehydrohalogenation o f f i -ch loroketon es The b e s t method fo r the dehydrohalogenation o f the /9 -chloroketon es in volved r e flu x ln g a v ig o ro u sly s tir r e d s o lu tio n o f sodium bicarbonate co n ta in in g th e f i -ch lo ro k eto n e. unsaturated ketone in good y i e l d . This method gave a c le a r , w ater-w hite Other methods which were tr ie d 4000 FREQUENCY C M -1 In fra re d 2000 of 2 -E th y lc y c lo p e n ta n o n e 1200 1000 - co NOISSIWSNVdl % (D if) rO OJ (n e a t), _o Spec tram 1500 0 ,0 3 1 900 800 mm, NaCl _0J c e ll. 700 37 o— H < co CVJ N O l S S I W S N V a i */« 38 in clu d ed d i s t i l l a t i o n from d im eth y la n ilin e, r e fiu x in g wi+h - sodium hydroxide s o lu tio n or a sodium carbonate s o lu tio n . These ).euiijis gave lower y ie ld s o f an in fe r io r product. b . Reduction o f the Unsaturated Ketones Raney n ic k e l as the c a t a ly s t and low pressure hydrogen (f?r 1 .) were found to g iv e a convenient method fo r reducing the doubl w ithout a f f e c t in g the carbonyl group. c . Chlorine A n alysis o f Chlorok- .ones Chlorine determ inations were mat oon as p o s s 'b le a f t e r d is ­ t i l l a t i o n o f th e sample, w hile the r e s u lt s were 0 .5 - ' % low, t h is may have been due in part to the method o f a n a ly s is , but more probably was t caused by th e i n s t a b i l i t y o f the c' . a sample o f f i -chloroketone to de _ *..ve bydrogd..* a f t e r standing a t room temperature f t i l l a t i o n and the y -chloroketone wc reason a l l the chloroketones were converter Tt was uncommon fo r ' de) sh ort time fo llo w s / r very q u ick ly , ^saturated or cy ketones as r a p id ly a; p o s s ib le . d . Dehydrohalogenation o f T -ch lo ro p ro p y l Ketones The b e s t metliod was th a t d escribed fo r 5-chloro-2-pentanone except th a t 10#, in stea d o f $0%s sodium hydroxide was u su a lly used. PART I I SYNTHESIS AND PROPERTIES OF DICYCLOPROPYL KETONE 39 INTRODUCTION This s e c tio n o f the t h e s is i s concerned with the sy n th esis and p r o p e r tie s o f d icy clo p ro p y l ketone ( i ) . D icyclopropyl ketone was of in t e r e s t as a p o s s ib le interm ediate in the preparation o f oth er d ic y c lo ­ propyl compounds. Furthermore, examination o f i t s absorption spectra and chem ical behavior might g ive a d d itio n a l inform ation concerning the conjugation o f the cyclopropane rin g with the carbonyl group. CHo 0 ^C H 2 r $ c H -8 -c sf| CHa CHg I C yclopropyl compounds resemble e th y le n ic compounds in some resp ects and both system s can en te r in to conjugation w ith other unsaturated groups. A cyclopropane rin g may conjugate with an eth y le n ic group,5 °,5 1 ,5 2 ,5 3 a carbonyl group^ 2 1 ,5 0 ,5 1 ,5U,55 a pheny i g r o u p o r a p y rid y l group^ and in th ese ca ses the observed s h i f t s o f absorption in the u lt r a v io le t have been a ttr ib u te d to p a r tic ip a tio n o f the cyclopropane rin g in hyper­ conjugation , A t y p ic a l example i s the work o f Rogers, who determined both the u lt r a v io le t sp ectra and d ip o le moments o f methyl isopropyl k eton e, methyl cyclop rop yl ketone and m ethyl v in y l k eton e. In both p h y sica l p rop erties the v alu es fo r methyl cyclopropyl ketone la y between the saturated and unsaturated k eto n e . The in crease in d ip o le moment over methyl isopropyl ketone was a ttr ib u te d to such forms as I I . 1*0 + C^^CH=C-CHa II Klotz determined the u lt r a v io le t absorption spectrum of i-c h o le sta n o n e ( i l l ) and found th a t the cyclopropane rin g produced a d is t in c t con ju gative e f f e c t . Carone (IV) a lso e x h ib its an u lt r a v io le t ab sorption spectrum very sim ila r to th a t o f i-c h o le s ta n o n e . CH3 CHa IV III HO Smith and R ogier sy n th esized 2-p henylbicyclopropyl (V) and determined the u lt r a v io le t spectrum. A comparison o f t h is spectrum ■with th a t o f phenylcyclopropane (VI) showed the two to be remarkably s im ila r . Also th e in fra red absorption sp ectra of the two showed many s im ila r itie s . From t h is data i t was concluded th a t, although one c y c lo ­ propane rin g conjugates w ith the benzene r in g , the second cyclopropane r in g does not en ter in to conjugation w ith 'th e f i r s t . V VI ia Eastman^ sy n th esized 1 -m eth y l-l* -iso p ro p y ltricy clo (k , 1 , 01 * ^ 2 heptanon-5 (V II ), to determine whether two cyclopropyl r in g s in a r ig id , p olar system could both e s ta b lis h a chain o f conjugation to the carbonyl group. He found th a t the u lt r a v io le t absorption spectrum o f the t r i ­ c y c lic ketone (VII) was not s ig n if ic a n t ly d iff e r e n t from th a t o f f i -dihydroum bellulone ( V I I I ) . VII VIII Chemical evidence fo r the conjugative e f f e c t of the cyclopropane rin g i s not la c k in g . The Michael r e a c tio n , which i s u su a lly a sso cia ted w ith a conjugated double bond, g iv e s 1 , 1 , h,U-tetracarboethoxybutane from 1 , 1-dicarboethoxycyclopropane. 60,65 8 CHg £ - 0 - E t | XC CH ^xC -0-Et 0 ^C -O -Et + Na-CH X C-O-Et 8 8 J-O -E t » ^CH CH2 C-O-Et I 0 I CH2 8 -O -iit C ^ £ -0 -E t 6 Also c e r ta in b ic y c lic terpenes con tain in g a cyclopropyl r in g , such as d - t h u j e n e , and ytf-carene, undergo the D ie ls - ild e r rea ctio n when reflu xed w ith m aleic anhydride .^ > 5 7 h2 The number o f other b icy clop rop yl compounds i s sm all. R ogier 6l Smith and ' prepared cyclop rop yl 2 -n itro -3 -p h e n y l-l-c y c lo p r o p y l ketone (IX) and succeeded in c r y s t a lliz in g two of the four p o ssib le racemic form s. CH^ 2 ^CH-CeHg | ^CH-C-CH | CH2 ^C H no 2 IX Murray and S tev en so n ^ and S la b ey ^ prepared spiropentane (X) from the r e a c tio n o f p e n ta e r y th r ity l tetrabromide with zin c in eth a n o l. GHoBr CH2 ----- CH2 I I B r-CH 2-C-C HUBr + 2 Zn _____ > CHgBr ./\ / CH2------CH2 S la b e y ^ produced d icyclop rop yl (Xl) from the rea c tio n of c y c lo ­ propyl ch lo rid e w ith lith iu m . CPU 2 | CH2 CH2 1 Li ^CH2 | 'SCH-CH | cuf ^CHa XI These sy n th eses o f d icyclop rop yl compounds a l l give low y ie ld s o f the d esired p rod u cts. U3 EXPERIMENTAL The p rep aration o f cL - a c e t y l- y -butyrolactone ch3- ch2 The procedure was analogous to th at used by Johnson, A s o lu tio n o f 320 g . o f sodium hydroxide in 810 m l. o f eth y l a lco h o l and 211(0 m l, o f water was cooled in an ic e bath to 5 ° . A cetoacetic e s te r (lOiiO g . , 8 m oles) was slo w ly added, and t h is was follow ed by 352 g. (8 m oles) o f eth y len e o x id e . hours. The s o lu tio n was s tir r e d a t 5° fo r 52 The base was n e u tra lize d w ith a c e tic acid and the s o lu tio n was ex tra cted w ith two o n e - lit e r p ortion s o f benzene. A fter the benzene had been removed th ere was obtained 590 g . (57$) o f d » -a c e ty l- T -bu tyro la c to n e, b .p . 115-130° a t 17 mm. This m aterial was used fo r the preparation of ■1O 5-chloro-2-pentanone w ithout fu rth er p u r ific a tio n . The preparation o f e th y l 3-cyclopropyl-3-ketopropanoatg | ' cuf 9, g ch- c - ch2- c- o- ch2- ch3 The procedure used was th at of Jackman, Bergman and A r c h e r ,^ except th a t Matheson sodium amide in heavy m ineral o i l was used in stea d of dry powdered sodium amide. To a s tir r e d suspension o f 200 g. ( 5 .1 moles) o f sodium amide in 1500 m l. o f eth er was slo w ly added 27h g . (3 .3 moles) o f methyl c y c lo ­ propyl ketone (prepared from 5-ch loro-2-p en tan on e). The s o lu tio n was r eflu x e d fo r 3° m in u tes, then cooled in an ic e bath and 781 g . ( 6 .6 m oles) o f d ie th y l carbonate was added dropw ise. The so lu tio n was reflu xed fo r two hours, cooled and 100 m l. o f methyl alco h o l was added to d estroy the e x c e ss sodium amide. The so lu tio n was added to 500 g . of ic e and then a c id if ie d w ith concentrated hydrochloric acid u n t il acid to Congo red paper. The eth er la y e r was separated and the water la y er was ex tra cte d w ith e th e r . The eth er s o lu tio n was washed once with w ater, once w ith 10$ sodium bicarbonate and then dried over calcium c h lo r id e . A fter removal o f the so lv en t there was obtained 376 g . (73$) o f e th y l 3-cyclop rop yl-2-k etop rop an oate, b .p . 92-105° a t h mm. The preparation o f d -cyclopropanecarbonyl- y -butyrolactone ch2- ch2 The procedure was e s s e n t ia lly th a t used by Adams and Vander Werf fo r the preparation o f d> - a c e t y l- y -v a lero la cto n e Sodium (52 g . , 2 .2 6 m oles) was d isso lv ed in one l i t e r o f absolute eth y l a lc o h o l and th e so lu tio n was cooled in an ic e b ath . Ethyl 3 -c y c lo - propyl-3-ketopropanoate was slow ly added, and t h is was follow ed by 130 g. (2 .9 5 m oles) o f eth y len e o x id e. The s o lu tio n was allow ed to come to room temperature w ith s t ir r in g fo r 22 hours. The alco h o l was removed in vacuo 1*5 and the resid u e d isso lv e d in 200 m l. o f "water. A cetic acid (ll*0 m l.) was added to n e u tr a liz e the b a se , and t h is was follow ed by s u f f ic ie n t s o lid sodium bicarbonate to n e u tr a liz e the excess a c e t ic a c id . t io n was ex tra cte d three tim es w ith 200 m l. of benzene. The so lu ­ A fter removal o f th e benzene th ere was d i s t i l l e d 36 g . o f recovered eth y l 3-cy clo p ro p v l3-ketopropanoate and 217 g . {69%) o f d* -cyclopropanecarbonyl- y -butyrola cto n e, b .p . 122° a t 3 mm., n ^ 1 ,U8Ul—1 . U8 I4U. A n al. C a lc 'd . fo r C6H10Oa : Founds C, 62.3; H, 6 .5 . C, 62.2$ H, 6.1*3. The 2 ,l*-dinitrophenylhydrazone was prepared and a fte r r e c r y s t a lli ­ za tio n from methyl a lco h o l m elted a t 17 5 -6 °. A n a l. C a lc 'd . fo r CMH14N406 : Found! C, 50.26; H, l*.19; N, 1 6 .7 5 . C, 50.62; H, 1*.39; N, 16.1*1. There was a lso c o lle c t e d 39 g . o f a lower b o ilin g liq u id , b .p . 1*7-57° a t 22 mm. This liq u id was r e d i s t i l l e d through a twenty place o 2^ column and a f r a c tio n was c o lle c te d b .p . 59 a t 32 mm., n^ l.l* 0 5 i* -l.1*058. The in fra red spectrum showed a strong hydroxyl absorption and a weak carbonyl band. A second fr a c tio n was c o lle c t e d , b .p . 73° a t 31 ron., nj^ 1 . 1*027 - 1 . 1*0 3 0 . The in fra red spectrum showed strong absorption a t 5 .7 8 yU ( e s t e r carbonyl) and a weak hydroxyl band. These products were not in v e stig a te d fu r th e r . The p reparation o f 1.7-dichloro-l*-heptanone from cL -cyclopropanec arb onyl - y ^ b u ty r o la c io ne . 8 ci-c h3- c h3- ch3- c- c h3- c h3- c h3- c i U6 To a one l i t e r three-necked f la s k f i t t e d w ith a s t ir r e r and a r e f lu x condenser was added 200 m l. o f concentrated hydrochloric a cid and 76 g . (0.1*93 m oles) o f c t -cyclopropanecarbonyl- 'y -bu tyro la c to n e. The s o lu tio n was s tir r e d u n t il the foaming had ceased and then i t was heated to b o ilin g . The s o lu tio n was co o led , saturated w ith ammonium ch lo r id e and ex tra cte d w ith three 100 m l. portion s o f eth e r . The como bined organic la y e r s were d ried a t 0 over sodium s u l f a t e . A fter removal o f the so lv e n t th ere was d i s t i l l e d 80 g . (88$) o f 1 ,7 -d ic h lo r o -liheptanone, b .p . 106-110° a t It mm., 1.1*731*. The 2 ,l*-dinitrophenyl- hydrazone was prepared and a f t e r r e c r y s ta lliz a t io n from methyl alco h o l m elted a t 7l*-5°. A nal. C a lc 'd . Founds fo r C13H16N40 4C13: C, 1*2.99; H, 1*.I*U; N, 15.U3; C l, 1 9 .5 2 . C, ltf.0 2 ; H, l*.l*3; N, 1 5.25; C l, 19.1*1*. The prep aration o f oxetone ( 1 . 1*; 1*. 7-dioxidoheptane) CHa-C H3-C Hg-C -C Ha-C Ha-C H3 To a 500 m l. three-necked f la s k f i t t e d w ith a s t ir r e r and a r e flu x condenser was added 200 m l. o f w ater, 10 m l. o f concentrated hydrochloric a cid and 1*7 g . ( 0 .3 1 mole) o f <1 -cyclopropanecarbonyl- *Y -b u ty ro la cto n e. The s o lu tio n was reflu x ed fo r 1*5 minutes and then steam d i s t i l l e d u n t il the d i s t i l l a t e was c le a r . The d i s t i l l a t e was saturated w ith potassium carbonate and the upper la y e r was separated and dried over potassium carbonate. The product was d i s t i l l e d from 70-170° a t 30 mm. and water hi was formed during th e d i s t i l l a t i o n . The s o lu tio n was again dried and there was d i s t i l l e d 23 g . (58$) o f oxetone (l,l+ jU ,7-d ioxid oh ep tan e), b .p . H9° a t 10 mm., n^ A nal. 1.14*60-1.L|i+61| ( l i t . v a lu e , b .p . 1 5 9 . 1) ° ) '.^ C alc*d. fo r C7Hla 0 2 : Found: C, 65.6; H, 9.U . C, 65.88; H, 9 .3 6 . P reparation o f 1.7-dichloro-l*-heptanone from oxetone Oxetone (22 g . , 0 .1 7 2 mole) in 20 m l. o f benzene was kept saturated w ith anhydrous hydrogen ch lo rid e fo r 90 minutes a t room tem perature. A fter removal o f the benzene there was d i s t i l l e d 3 g . of recovered oxetone and 21 g . (79$) o f 1 ,7 -d ich loro-li-h ep tanone, b .p . IOI-IOI40 a t 3 mm. Its 2 ,U~dinitrophenylhydrazone m elted a t 7U-5° and a mixed m elting poin t w ith an au thentic sample showed no d ep ression . Preparation o f 1 .7-d ich loro-li-h ep tan on e from *¥ -butyrolactone 69 In a one l i t e r three-necked f la s k f i t t e d w ith a r e flu x condenser, s t i r r e r , and a d d itio n fu n n el there was d isso lv e d 23 g . ( l mole) of sodium in 1*00 m l. o f a b solu te methyl a lc o h o l. The s o lu tio n was cooled and 172 g . (2 m oles) o f *Y -b utyrolacton e was added and the s o lu tio n was reflu x ed th ree hours. The so lv en t was removed in vacuo. The f la s k was cooled and 500 m l. o f concentrated hydrochloric acid was slo w ly added w ith vigorous s t i r r i n g . c o o le d . The s o lu tio n was reflu x ed fo r 15 m inutes and Ether (100 m l.) was added and the upper la y e r was separated and th e water ex tra cted w ith e th e r . potassium carbonate. The organic la y e r s were dried over A fter removal o f the so lv e n t there was d i s t i l l e d k8 119 g . (66#) o f l,7 -d ich lo ro -i* -h ep ta n o n e, b .p . 9l*-98° a t 2 mm. Its 2 ,l*-dinitrophenylhydrazone melted a t 7l*-$° and a mixed m eltin g p oin t w ith an a u th en tic sample showed no d ep ression. Preparation o f d icyclop rop yl ketone To a one l i t e r three-necked f la s k f i t t e d w ith a r e flu x condenser 1Q and a m etal Hershberg s t ir r e r there was added 600 m l. o f 20# sodium hydroxide and 16$ g . ( 0 .9 mole) o f 1 ,7 -dich loro-li-hep tanone. The mixture was reflu x ed fo r 30 m inutes w ith vigorous s t ir r in g , then steam d i s t i l l e d u n t il the c h a r a c te r is tic odor o f d icyclop rop yl ketone was absent from the d i s t i l l a t e . The d i s t i l l a t e was then saturated with potassium carbon­ a t e , the upper la y e r separated and the water la y e r extracted once w ith e th e r . The combined organic la y e r s were dried over potassium carbonate. I f t e r removal o f the eth er th ere was d i s t i l l e d 69 g . (70#) o f d ic y c lo propyl k eto n e, b .p . 69° a t 20 mm., nQ 1.1*61*8-1.1*6$!*. I n a l. C a lc 'd . fo r C7Hlo 0: Found: C, 76.1*; H, 9 .1 . C, 7 6 .18; H, 9 .1 3 . The 2,l*-dinitrophenylhydrazone was prepared and a f t e r r e c r y s ta lliz a t io n from methyl a lc o h o l melted a t 192°. A nal. C a lc 'd . fo r C13H14N40 4 : Found: C, $3.79; H, 1*.86; N, 1 9 .3 0 . C, $3.81*; H, $.01*; N, 1 8 .8 2 . U9 The preparation o f dicyclopropylketoxim e PE CEK h ch2 I ^CH-C-dH I CE' ^CH 2 D icyclopropyl ketone (21 g . , 0.19 m ole), 20 g . of hydroxylamine hydrochloride, 17 g . o f sodium bicarbonate and 60 m l. o f water were heated on a steam bath with s t ir r in g fo r s ix hours. The so lu tio n was co o le d , the upper la y e r sep arated , and the water la y e r extracted w ith e th e r , -ifte r drying over potassium carbonate the eth er was removed and the resid u e was r e c r y s ta lliz e d from petroleum e th e r . There was obtained 19 g . (62%) o f d icyclopropylketoxim e, m .p. 7 7 °. I n a l. C a lc 'd . fo r C7H1XN0: Found: C, 67.2; H, 8 .8 ; N, 1 1 .2 . C, 6 7 .0 , 67.22; H, 8 .9 7 , 8.98; N, 1 0 .8 9 , 1 0 .8 0 . The Beckmann rearrangement o f d icyclop ropyl ketoxime CH2 | S ch2 H Q ^ ch2 dh-m- c- ch ^ ch2 I The procedure was analogous to th a t used by Roberts and Chambers 70 fo r methyl cyclop rop yl ketoxim e.' To a 900 m l. three-necked f la s k f i t t e d with a r e flu x condenser, s t i r r e r and a d d itio n fu n n el there was added 10 g . o f dicyclop rop yl ketoxim e, 16 g . o f sodium b icarb on ate, 69 m l. o f water and UO m l. o f d ioxan e. The s o lu tio n was heated to b o ilin g and 16 g . of b enzenesulfonyl ch lo rid e was added over ten m in utes. The so lv en t was removed on a steam £0 bath and th e s o lid resid u e was extra cted w ith eth er in a Soxhlet fo r four hours. A fter removal o f the ether there was obtained 6 .5 g . (65$) o f N -cyclopropyl-cyclopropanecarboxam ide. m.p. 1110 . A nal. A p ortion was e a s il y sublim ed, The compound could a lso be r e c r y s ta lliz e d from cyclohexsane. C a lc 'd . fo r ^H^NO: Founds C, 67.2; H, 8.8; N, 1 1 .2 . C, 6 8 .0 2 , 67.78; H, 9.06 , 8.83; N, 10.6U , 10.9*1. Preparation o f cyclopropanecarboxamide The procedure o f S c h la tte r was used. 71 Cyclopropanecarbonyl ch lorid e (60 g . , 0 .5 8 mole) was d isso lv e d in 500 m l, o f e t h e r . w ith ammonia. The s o lu tio n was cooled in an ic e bath and saturated The eth er was removed and the resid u e was extra cted w ith chloroform in a Soxhlet fo r eig h t hou rs. d ried overnight a t 7 0 °. The c r y s ta ls were f il t e r e d and There was obtained hO g . (82$) o f cyclopropane- carboxamide, m .p. 12 U-125 ° . Preparation o f cyclopropylamine CHa | 5 ch- nh3 CHjf The procedure of Lipp, Buchkremer and S eeles was used 51 Sodium (16 g .) was d isso lv e d in 300 m l. o f methyl a lco h o l and 3^ g» o f cyclopropanecarboxand.de was added. s o lu tio n was reflu x ed fo r one hour. o f ic e water was added. Bromine (55 g .) was added and the The so lv en t was removed and 150 m l. The so lu tio n was saturated w ith potassium carb on ate, th e upper la y e r was sep arated , and the water la y er extracted w ith e th e r . The eth er was removed and 29 g . of N -cyclopropyl-O -m ethyl- urethane was d i s t i l l e d b .p . 69-79° a t 3 mm. The urethane was added to 100 m l. o f 75# sodium hydroxide and the cyclopropylam ine was steam d is ­ t i l l e d in to 100 m l. o f 6 N hydrochloric a c id . a steam b ath . The water was removed on Twenty m i l l i l i t e r s o f 50# sodium liydroxide was added to the cyclopropylamine hydrochloride and the cyclopropylamine was d i s t i l l e d , b .p . 1*9-52°. I t was then d ried over barium oxide fo r four hours and r e ­ d i s t i l l e d , y ie ld in g 10 g. o f cyclopropylam ine, b .p . 5 0 -5 1 °. Preparation o f N-cyclopropyl-cyclopropanecarboxam ide from c y c lo ­ propyl amine and cyclopropanecarbonyl ch lo rid e Cyclopropylamine (5 g .) was d isso lv e d in 20 m l. o f p yrid in e and cooled in an ic e b ath . Cyclopropanecarbonyl ch lo rid e was added dropwise and the s o lu tio n was allow ed to stand overnight a t room tem perature. The s o lid was f i l t e r e d and dried in a d esic c a to r over phosphorus pentoxide to remove the p y r id in e . The s o lid was extracted w ith eth er and the amide was p r e c ip ita te d by co o lin g in a dry ic e b ath. Four grams o f N -cy clo - propyl-cyclopropanecarboxamide was ob tain ed , which, when r e c r y s ta lliz e d from cycloh exan e, m elted a t 111°. The mixed m eltin g p oin t w ith a sample prepared from the rearrangement o f dicyclopropylketoxim e showed no d ep re ssio n . 52 The preparation o f the hydrazone and azine o f d ic (y clopropyl ketone , nh2 CH3-CH3 C^2-PH2 CH CH C=N-N = { c % -c u z ch2- ch2 To a 500 m l. three-necked fla s k f i t t e d w ith a r e flu x condenser and s t i r r e r there was added UO g . (O.36 I1 mole) of d icyclop rop yl k eton e, UO g , o f 85$ hydrazine hydrate, 2 m l. o f a c e tic a cid and 100 m l. of e th y l a lc o h o l. The s o lu tio n was heated 30 minutes a t 90° and the a lco h o l was then removed by d i s t i l l a t i o n . a t 120° and then d i s t i l l e d . The residue was heated fo r three hours There was obtained 25 g . (56$) o f d ic y c lo ­ propyl ketone hydrazone, b .p . 100-115° a t 6 mm. and 17 g . (W $) o f d icy clop rop ylk etazin e b .p . 127 - 13 h° a t 2 mm., which s o lid i f i e d a t once. A fter r e c r y s t a lliz a t io n from methyl a lco h o l i t m elted a t 9 2 -3 °. A n a l. C a lc'd . fo r C14H20N2: Founds C, 7 7 . 8 ; H, 9 .3 ; N, 1 2 .9 5 . C, 77.70; H, 9.55; N, 1 2 .2 k . The preparation o f dicyclopropylmethane from d icyclopropylketone hydrazone ...... - r — CH2 I ^ ch2 'C H -C H j-C H | OHJ X CH3 Sodium (2 g .) was d isso lv e d in 100 m l. o f d ieth y len e g ly c o l and 25 g . (0 .2 mole) o f d icyclopropylketone hydrazone was added. The s o lu ­ tio n was heated to 190 - 210 ° fo r U5 minutes and the product was d i s t i l l e d as formed. There was given o f f k .2 l i t e r s o f n itrogen (a s measured by 53 a "Wet T est M eter). and r e d i s t i l l e d . b .p , 102 o A nal. The d i s t i l l a t e was dried over potassium carbonate There was obtained 9 g . (hl%) o f dicyclopropylm ethane, 25 a t atmospheric p r essu re, n^ 1 . 24228, C a lc'd . fo r C7HX2: Found: C, 87.1*5 H, 1 2 .6 . C, 87.72; H, 12.1*3. Preparation o f dicyclopropylm e thane by the Huang-Minlon procedure 73 D icyclopropyl ketone (35 g . , 0 .3 2 m o le), 300 ml. o f d ieth ylen e g ly c o l, hO g . o f potassium hydroxide and hO m l. o f 85$ hydrazine hydrate were heated one hour a t 130°. The excess hydrazine and the water were d i s t i l l e d u n t i l the pot temperature reached 180 ° , where i t was main­ tain ed u n t i l a l l the product had d i s t i l l e d . The d i s t i l l a t e s were com­ b in ed , th e upper la y e r separated and the water la y er ex tra cted w ith e th e r . The combined organic la y e r s were dried over potassium carbonate and cupric s u lf a t e . A fter removal o f the so lv e n t there was d i s t i l l e d 19 g . ( 63 $) o f dicyclopropylroethane, b .p . 102 ° , n ^ 1.U228. The preparation o f d icy clop rop ylcarb in ol H CHo 0 ^CHa I 'CH-d-CH | CH/ H X CHa To a one l i t e r three-necked f la s k f i t t e d with a r e flu x condenser, s t i r r e r and an a d d itio n funnel there was added 6 g . o f lith iu m aluminum hydride and 250 m l. o f e th e r . D icyclopropyl ketone (Uh g . , O.h mole) was added dropwise over a period of 30 m inutes and the s o lu tio n was r eflu x e d one hour lo n g e r . The mixture was cooled in an ic e bath and 20 m l. o f water was added s lo w ly . Concentrated sodium hydroxide (12 N) was added to d is s o lv e the aluminum hydroxide, the upper la y er was separated and the water la y e r extracted with e th e r . la y e r s were d ried over potassium carbonate. The combined organic A fter removal o f the s o lv e n t, th ere was obtained UO g . (89%) o f d icy clo p ro p y lca rb in o l, b .p . U8° a t 3 mm., . A n al. I.U 627 - I .I 463O. C a lc'd . fo r C7Hla0 : Founds C, 7U.9U; H, 1 0 .7 6 . C, 75.02; H, 1 0 .7 5 . U ltr a v io le t Spectra The u lt r a v io le t sp ectra o f d iiso p ro p y l k eton e, isop rop yl cyclopropyl k eto n e, d icyclop rop yl ketone and isopropenyl cyclopropyl ketone were run in 9$% e th y l a lc o h o l. A Beckmann Model DU spectrophotom eter was used w ith one cm. quartz c e l l s . The isopropenyl cyclopropyl ketone (se e page 2 3 ) was fr e s h ly d i s t i l l e d b efore being u sed . The e x tin c tio n c o e f f ic ie n t s are given on the fo llo w in g page. Infrared Spectra The in fra r ed sp ectra o f d icyclop rop yl k eton e, d icy clo p ro p y lca rb in o l, dicyclopropylm ethane, isopropenyl cyclopropylketone and 1 , 7 -d ic h lo r o -h heptanone were run in a Perkin-Elmer Recording Infrared Spectrophotom eter, Model 21 u sin g sodium ch lo rid e c e l l s . pages 56 to 6 0. The sp ectra are reproduced on I l l sp ectra were determined on th e pure liq u id s in c e l l s o f 0 . 03 I mm. th ic k n e s s . 55 EXTINCTION COEFFICIENTS OF THE SEVERAL KETONES ItijA 208 210 212 215 218 220 222 225 230 235 2l*0 2U5 250 255 260 26h 265 266 268 270 27l* 275 276 278 280 282 281* 285 286 288 290 295 300 305 310 315 320 330 3JU0 D iisop rop yl Ketone Isopropyl Cyclopropyl Ketone D icyclopropyl Ketone 1,118 803 2,122 2,029 278 800 3 72 192 3 3 2 2 3 5 8 11 17 7 7 5 8 12 17 22 23 15 28 20 32 3h 35 35 wax. 35 3fc 27 27 28 28 wax. 28 28 27 25 20 15 10 \ 11 16 22 28 33 35 36 36 max. 36 35 Isopropenyl Cyclopropyl Ketone 9,1*16 1 0 , 01*1 10,289 wax. 10,195 9 ,9 60 9 ,1 2 1 6,998 1*,352 2,028 71*6 215 22 11 11 32 11* 26 18 31 19 23 25 18 12 12 7 3 29 33 37 39 max. 39 36 33 23 12 S6 o— o— o— C o v> w -p b oA u g4 © rH £o — OD o_ V) FREQUENCY CM z o (to N O tS S IflS N V H l % £7 o— o— o— o_ 1 _o 0 ■s 0 t o_ 1 o -oo o •H Q o_ -(0 o_ o a: o CM 5 oz Z> 0 _ O o > < 5 ID in ^ ro N O ISSIW SN V B i % oo 58 o— o— o— -0 0 O •H Q o_ FREQUENCY CM~ CM o_ ID in ^ ro NOISSI W S N V a i % $9 o— o— o— o_ G O 0) w -P -C D oPi & o rH & o & 0) p. E oPi 10 H o_ in CM o_ a=> o° 00 to in a 0 a 3 Pc Ji 1 -ct I o h o o_ CM -CO •H o_ o_ o CM if) z o CH-C-CH~ r.vr CHa 8 ^ ch2 I ^ C H -C -C H I CH2 ^CHa Proposed Synthesis fo r D icyclopropyl Ketone Methyl cyclop rop yl ketone condensed w ith d ie th y l carbonate in the presence o f base to g iv e the known e th y l 3 -cy clo p ro p y l- 3 -ketopropanoate in good y ie ld . The l a t t e r , on treatm ent w ith ethylene o x id e , gave the expected ( t -cyclop rop anecarb on yl-'}'-bu tyrolactone. This compound gave the co rrect elem ental a n a ly s is , as d id i t s 2 ,ii-dinitrophenylhydrazone. When cL -cyclopropanecarbonyl-'}'-butyrolactone was trea ted w ith 6N hydrochloric a c id , two products were o b tain ed , n e ith e r o f which c o r r e s­ ponded to the e x p e c t e d - c h io r o p r o p y l cyclopropyl k eton e. The low er b o ilin g product d id n ot con tain ch lorin e and i t s in fra red spectrum did not show the presence o f a carbonyl or hydroxyl group, or a double bond. A n a ly sis showed the em p irical formula to be C7 H120 2 . This a n a ly s is , and 63 subsequent r e a c tio n s were c o n s is te n t w ith the form ulation o f t h is product as oxetone (l,lijU ,7 -d io x id o h e p ta n e ). By reaction o f oxetone w ith anhy­ drous hydrogen ch lo rid e in benzene, a compound id e n tic a l w ith the higher b o ilin g fr a c tio n was ob tain ed . The higher b o ilin g f r a c tio n gave a ch lo rin e a n a ly sis which was somewhat low fo r C7H120C12 . I t s in frared spectrum had a symmetrical peak fo r the carbon-hydro gen s tr e tc h in g , and showed th a t the m olecule contained a carbonyl group and carbon-chlorine bonds. The 2 ,h-dinitrophenylhydrazone analyzed c o r r e c tly fo r C13H16N404C12 . Upon dehydrohalogenation, the chloroketone y ie ld e d a ketone which was la t e r shown to be d icy clo p ro p yl ketone. This a n a ly sis and rea ctio n were c o n s is te n t w ith th e form ulation o f t h is product as 1 ,7 -d ich lo ro -ii-h ep ta n o n e. The course o f th e rea ctio n could now be w r itte n as fo llo w s: ,0— CH. i n mi mi 1 2 N H31 c h 2- c h 2- c h 2- c - c h 2 - c h 2- c h : Cl Cl When concentrated hydrochloric acid was u sed , only 1 ,7 -d ic b lo r o -h heptanone was obtained; w ith IN hydrochloric acid on ly oxetone was ob ta in ed . The fo reg o in g procedure was lon g and ted iou s and the sy n th e sis of the s ta r tin g m a te r ia l, methyl cyclopropyl ketone, required sev era l s te p s . This method, th e r e fo r e , had l i t t l e to recommend i t . I t was now apparent, however, th a t a simple and d ir e c t sy n th e sis o f d icyclop rop yl ketone was a t hand, fo r i t had been reported th a t when two moles o f > '-b u ty ro la cto n e were condensed in the presence o f a b a sic /T O c a t a ly s t and then reflu xed w ith d ilu te a c id , oxetone was formed, y -B u ty r o la c to n e was condensed w ith i t s e l f to give dibutyrolactone and t h is product w ithout i s o l a t i o n , was trea ted w ith concentrated hydro­ c h lo r ic acid to g iv e 1,7-d ich loro-U -h ep tan on e. This product was id e n ti­ c a l w ith th a t prepared from c t -cyclopropanecarbonyl-y -butyrolac to n e , both by the m eltin g p o in t and mixed m eltin g p oin t o f i t s 2 ,li-d in itr o p henyl hydraz o n e . 8 CHa— C I 8 CH2— C ==C— C. 'o -> I CH2-C h£ 'o I 0 7^0 Gl-C H2-CH2-CH2-C-C H2-C H2-C Ha-Cl CH3-CH2 CHa-CHg I t was e a s ily dehydrohalogenated to give dicyclop rop yl ketone. This sequence o f re a c tio n s provided a very convenient method fo r preparing d icyclop rop yl ketone in good y ie ld from the e a s ily a v a ila b le and cheap *Y -b u ty r o la c to n e. The fo llo w in g method was used to prove the stru ctu re of d ic y c lo ­ propyl ketone. 65 j 'CH-S-CH | cftT v c CH-NE CHa 0 | M3H-C-C1 CH2 | ^CH-NH- > D icyclopropyl ketoxime was prepared from d icyclop ropyl ketone and hydroxylamine. On treatm ent w ith ben zen esu lfon yl c h lo r id e , the oxime underwent a Beclanann rearrangement to give N-cyclopropylcyclopropanecarboxam ide. This compound was a lso prepared from cyclopropylamine and cyclopropanecarbonyl c h lo r id e . The tw> were proved to be id e n t ic a l by m elting p oin t and mixed m eltin g p o in t. D icyclop rop ylcarb in ol was prepared by reduction o f dicyclop rop yl ketone w ith lith iu m aluminum hydride. Dicyclopropylmethane was prepared by the Huang-Minlon m o d ifica tio n o f th e W olff-K ishner red u ctio n . The hydrazone o f d icy clo p ro p y l ketone and d icyclop rop ylk etazin e were prepared from d icyclo p ro p y l ketone and hydrazine. The u lt r a v io le t sp ectra of d iiso p ro p y l ketone ( i ) , iso p ro p y l c y c lo propyl ketone ( I I ) , d icyclop rop ylk eton e ( I I I ) , and isop rop enyl c y c lo propyl ketone (IV) were run in 95% eth a n o l, and are shown on page 66. 2 l3 (II) (IV) IV Diisopropyl Ketone II Isopropyl Cyclopropyl Ketone III Dicyclopropyl Ketone IV Isopropenyl Cyclopropyl Ketone ,111 ‘ II II IV III 220 240 260 /*) M- 280 300 320 67 max The u lt r a v io le t sp ectra o f isop rop yl cyclopropyl k eton e, A a le max ^ 2 0 8 ( € > 1 ,1 1 8 ), 276 35 ) and dicyclopropyl k eton e, A a le X 208 (£ >■ 2 ,1 2 2 ), 266 ( £ 36) were very sim ila r to each o th er. The max u lt r a v io le t spectrum o f isopropenyl cyclopropyl k eton e, ^ .a l c 218 {6 1 0 ,2 8 9 ), 305-310 ( 6 3 9 ), was n early id e n tic a l w ith other i s o max propenyl ketones such as methyl isopropenyl ketone A. a le 218 ( £ 8 , 300 ) , max 319 2 6 .5 ) and e th y l isopropenyl k eton e, A a lc 220 7 , 880 ) , 320 ( £ 27 ) . ^ I t would appear th at although one cyclopropane rin g can conjugate w ith a carbonyl, a second such rin g on th e other sid e o f the carbonyl has o n ly a very s li g h t bathochromic e f f e c t . This i s analogous to the r e la tio n s h ip between the spectra of c t >/3 -unsaturated ketones and 4 , 9 4# f t '-d iu n satu rated k eto n es. PART I I I MISCELLANEOUS 68 DISCUSSION T his s e c tio n con tain s some m iscellaneous experiments re la te d to the chem istry o f the cyclopropyl group, some o f which have on ly an in d ir e c t b earing on the main body o f the t h e s is . I t was d esira b le th at the exp eri­ mental d e t a ils be included in t h is t h e s is . The only experiments in t h is group which req u ire d iscu ssio n are those p erta in in g to a reported synthe­ s is of -b u tyrolac to n e . As p art o f a stu d y on the preparation o f c e r ta in la c to n e s , an attempt was made to prepare ^ -butyrolactone, by the method of Raha. 18 The r e a c tio n was p ictu red by Raha as fo llo w s: J-O-Bt CH2 N C-O-Et J to -l ^C-O-Et + A1C13- ^ - CH N£-Q-Et + + A1C12+ + H31 (ev o lu tio n ) ch2- ch2 c h 2— c I c h 2- c h £ 1131 « ---------* c -o -st a i c i 2- o - c h 2- c h 2 - c h ^ -o -st Raha*s procedure i s e s s e n t ia lly as fo llo w s: malonic e s t e r , in chloroform , was slo w ly added to anhydrous aluminum ch lo r id e , lydrogen ch lo rid e being ev o lv ed . Ethylene oxide was then slow ly added to the so lu tio n a t room temperature. A fter a d d itio n was com plete, the mixture was a c id if ie d with 5N hydrochloric a c id and reflu x ed fo r f iv e to u r s . The so lu tio n was 69 cooled and ex tra c te d with benzene. A fter removal o f the benzene, i t was reported th at th ere was obtained a q u a n tita tiv e y ie ld o f - b u t y r o l a c t o n e , b .p . 85-110° a t 11 mm., n ^ 1 .3 7 6 0 . This m aterial was reported to give a co rr ec t elem en tal a n a ly sis and n eu tr a liz a tio n eq u ivalen t fo r "y -butyrola c to n e . Raha rep orts th at 11the liq u id ¥ -la c to n e which b o ile d u su a lly over a range could be c o lle c te d in two d is t in c t ly d iffe r e n t fr a c tio n s which had the same con ten ts o f carbon and hydrogen and same sa p o n ific a tio n e q u iv a le n t. On by Sueur. This property i s p o ssib ly due to a dimorphism as suggested . . . . In more or l e s s id e n tic a l y ie ld the two fr a c tio n s gave a 2 ,U -dinitrophenylhydrazide m .p. 93-U °." A co rrect a n a ly sis was rep orted . When t h is r e a c tio n was repeated fo llo w in g Raha *s procedure e x a c tly , two fr a c tio n s were obtained w ith b o ilin g p o in ts corresponding to those given by Raha. The f i r s t f r a c t io n , however, was shown to be recovered malonic e s te r by comparison o f i t s in frared spectrum w ith the spectrum o f an au thentic sam ple. A ls o , a comparison o f t h is spectrum with the spectrum o f au th en tic ^ -b u ty r o la c to n e stowed the two to be d is t in c t ly d if f e r e n t . The second fr a c tio n contained c h lo r in e . The reaction was run again u sin g f i v e moles o f malonic e s te r to ob tain a la r g e r amount of the second fr a c tio n and the r e flu x in g w ith 5N hydrochloric a cid was o m itted . When the product was d i s t i l l e d , three fr a c tio n s were obtain ed , the f i r s t two corresponding to those p rev io u sly obtained and the th ird b o ilin g somewhat h igh er. C7Hi ;l0 4C1. F ra ctio n two gave an elem ental a n a ly sis fo r The th ird fr a c tio n a lso contained c h lo r in e . A ll three fr a c tio n s gave the same amide, which did not contain c h lo r in e , when 70 tr ea te d with concentrated ammonia. This amide proved to be malonamide by m eltin g p oin t and mixed m eltin g poin t with an au thentic sample. Dibromomalonamide prepared from these samples a lso had the co rrect m eltin g p o in t. F raction two and urea gave b arb itu ric a c id , which had the c o r r e c t m eltin g poin t and elem ental a n a ly s is . e th y l e th y l malonate and b i s - F in a lly , / i -c h lo r o - -ch lo r o eth y l malonate were prepared by e s te r interchange from malonic e s te r and ethylene chlorohydrin. Their in fra r ed sp ectra were compared with the sp ectra o f fr a c tio n s two and three r e s p e c tiv e ly . They were found to be id e n t ic a l. Therefore the products from the rea ctio n o f malonic e s t e r with eth ylene oxide in the presence o f aluminum ch lorid e a r e /S -ch lo r o eth y l eth y l malonate and b i s - f i -ch lo r o eth y l m alonate. was ob tain ed . No~y -butyrolactone 71 EXPERMENTAL - The R eaction o f Malonic Eater -with Ethylene Oxide in Presence o f Aluminum Chloride' 7 ft This procedure was analogous to th a t of Raha .' To a two l i t e r three-necked f la s k f i t t e d w ith a s t ir r e r and a d d itio n funnel th ere was added 665 g. (5 moles) o f aluminum c h lo r id e . Malonic e s te r (800 g . , 5 m oles) in one l i t e r o f chloroform was added with c o o l­ in g and vigorous s t i r r i n g . The ic e bath was removed and the so lu tio n was s tir r e d u n til a l l the aluminum chlorid e liad d iss o lv e d . The s o lu ­ tio n was cooled and 220 g . (5 m oles) of eth ylen e oxide was added as a gas keeping the temperature below 20 °. The ic e bath was removed and the s o lu tio n was s tir r e d a t room temperature fo r 1*2 to u r s . D ilu te hydrochloric acid (1500 m l. o f £N) was added and the s o lu tio n s tir r e d u n til th e p r e c ip ita te d iss o lv e d . The chloroform la y er was separated and d ried over potassium carbonate. A fter the chloroform had been removed in vacuo there was obtained 501* g . of recovered malonic e s t e r , b .p . 60-61 o 25 a t 1 mm,, n^ 1.1*128. I t s in frared spectrum was id e n tic a l with the spectrum o f an au thentic sample. There was a lso obtained 192 g . o f f i -c h lo r o e th y l e th y l m alonate, b .p . 105 a t 1* mm., nj^ 1.1*358-1.1*1*02. The a n a ly tic a l sample had nj^ 1.1*386 ( l i t . v a lu e , b .p . 105-6° a t 3 m m .).^ Anal. C a lc fd . fo r C ^ j O ^ l : Found: C, 1*3.2; H, 5 .7 ; C l, 1 8 .2 . C, 1*3.82, l*i*.08; H, 5 .6 8 , 5.9l*; C l, 1 7 .2 , 1 7 .0 8 . The high carbon and low clilo rin e an alyses can be accounted for by con­ tam ination w ith about 5% o f malonic e s t e r . The a n a ly sis i s included 72 p r in c ip a lly to show th a t the product contained c h lo r in e . There was a ls o obtained U5 g . o f b i s - ^ -ch lo ro eth y l m alonate, b .p . 136-151° a t 25 It «m. I.lt6 2 5 -l.ii6 1 ^ ( l i t . v a lu e s , b .p . lU 2-3° a t 3 mm., 16U° a t i s mm, ™ 3) . ? 9 »82 15 The r e a c tio n o f /B -c h lo r o eth y l eth y l malonate with urea The procedure was analogous to that of Dickey and Gray. Ro To a 500 m l, three-necked f la s k f i t t e d with a r e flu x condenser, s t i r r e r and a d d itio n funnel were added 75 ml. of ab solu te e th y l alcoh ol and 5 g . o f sodium. Then 20 g . of -ch lo r o eth y l e th y l malonate and 6 g . o f urea in 75 m l. o f hot a lcoh ol was added and the so lu tio n was reflu x ed o v ern ig h t. The s o lu tio n was cooled and 100 ml. o f water and 10 m l. o f concentrated hydrochloric acid were added. The so lu tio n was cooled in a dry ic e bath and the s o lid was f il t e r e d o f f . A fter . r e c r y s t a lliz a t io n from hot water there was obtained two grams of o b a r b itu ric a cid ,m .p . 253 . A sublimed sample had a m elting p oin t of 256° ( l i t . v a lu e , 2h 5°).^ 2 A nal. C a lc1d . fo r Found: -c h lo r o e th y l eth y l malonate w ith ammonia -c h lo r o e th y l e th y l malonate was added to 60 m l. of concentrated ammonium hydroxide m inutes. N, 2 1 .9 . C, 37.52; H, 2.82; N, 2 1 .8 2 . The r e a c tio n o f Ten grams o f C, 37.5; H, 3.11; and the mixture was shaken for f if t e e n The s o lu tio n was allowed to stand fo r an hour, then cooled and f i l t e r e d . A fter r e c r y s ta lliz a t io n from hot water there was obtained 97 g . (86$) o f malonamide, m .p. 168-9° ( l i t . v a lu e, 1 7 0 °). A mixed 73 m eltin g p o in t w ith a sample prepared from d ie th y l malonate showed no d ep ressio n . The r e a c tio n of malonamide w ith bromine The procedure o f Backes, West and W hitely was u sed. ft! A sm all sample of malonamide (from f i -c h lo r o eth y l e th y l malonate) was d iss o lv e d in hot water con tain in g some sodium a c e ta te . Enough bromine was added to the warm s o lu tio n to keep i t saturated fo r 15 m inutes. The bromine was evaporated, the s o lu tio n was cooled and the s o lid f i l t e r e d . There was obtained dibromomalonamide, m.p. 201-2 Q ( l i t . v a lu e , 2 0 3 ° ) .81 The r e a c tio n o f b i s - jfi -c h lo r o eth y l malonate with ammonia Ten grams o f b is -/^ -c h lo r o e th y l malonate and ijO m l. o f concentrated ammonium hydroxide were shaken fo r 15 m inutes. to stand fo r one hour, cooled and f i l t e r e d . The s o lu tio n was allowed A fter r e c r y s ta lliz a t io n from hot-w ater there was obtained three grams o f malonamide, m.p. 1 6 5 -6 °. A mixed m eltin g p o in t with a sample prepared from malonic e s te r showed no d ep ressio n . The preparation o f / f -c h lo r o e th y l eth y l malonate and b is -/^ -ch lo ro ­ e th y l malonate from malonic e s ie r ana eth ylen e chlorohydrin The procedure was th a t o f Michael and Weiner. 79 Ten grams o f anhydrous hydrogen ch lorid e was passed in to a s o lu tio n o f 100 g. o f eth ylen e chlorohydrin and 160 g. o f malonic e s te r in a 500 m l. round-bottomed f la s k . The s o lu tio n was allowed to stand for 2h 7h hours a t room tem perature. A fter d i s t i l l a t i o n through a column, there was obtained 80 g . o f recovered d ie th y l m alonate, 5U g. o f ^ -ch lo r o eth y l eth y l m alonate, b .p . 106 o23 a t I4 mm., rip l.lj.379-l.UkOO, and 15 g. of b i s - ^ -c h lo r o e th y l m alonate, b .p . ll±0-lU6° a t k mm., 1 .U622- 1 .U6 U2 The in fr a r e d sp ectra o f both / 6 -ch lo ro eth y l eth y l malonate and b is-y ^ -c h lo r o e th y l malonate were compared with the spectra of the corresponding compounds prepared from malonic e s t e r , ethylene oxide and aluminum c h lo r id e . They were found to be id e n t ic a l. P reparation o f m ethylphenylcyclopropylcarbinol In a three l i t e r three-necked fla s k f i t t e d with a condenser, s t ir r e r and a d d itio n funnel was placed 27 g . (1.12 moles) o f magnesium. Bromobenzene (170 g . , 1.08 m oles) in one l i t e r of eth er was slow ly added and the s o lu tio n was reflu x ed 30 m inutes. Methyl cyclopropyl ketone (81i g . , 1 mole) in 200 m l. o f ether was slow ly added. The s o lu ­ tio n was reflu x ed one hour, then cooled in an ic e bath and hydrolyzed with 200 m l. o f satu rated ammonium c h lo r id e . The ether la y e r was separated and the water la y e r extracted w ith e th e r . organic la y e r s were dried over sodium s u l f a t e . The combined After removal o f the s o lv e n t, th ere was obtained 130 g . (80$) o f m ethylphenylcyclopropylc a r b in o l, b .p . 90° a t 1 mm., n^° 1.£369-1.5377 ( l i t . v a lu e , b. p. 119-21 a t 15 mm. ) 75 Preparation o f 5-ch loro-2-ph enyl-2-p entene CH3-C=CH-CH2,-C H2-C1 C6H6 To a 500 m l. three-necked f la s k f i t t e d with a condenser, s t i r r e r , and a d d itio n fu n n el there was added 112 g . o f phosphorus tr ic h lo r id e . The f la s k was cooled in an ic e bath and 61* g . (0.1* mole) o f m ethylp h en ylcyclopropylcarbinol was added. The ic e bath was removed and the s o lu tio n s tir r e d a t room temperature fo r s ix hours. Then 100 m l. o f chloroform was added, follow ed by 200 m l. o f ic e w ater, and the so lu tio n was s tir r e d fo r 30 m inutes. The chloroform la y er was separated and the water la y e r ex tra cted once w ith $0 m l. o f chloroform. The chloroform la y e r s were washed with a 10# sodium carbonate s o lu tio n and dried over sodium s u lf a t e . I f t e r removal o f the chloroform ,’ th ere was obtained 51 g . (71#) o f supposedly 5-ch loro-2-p h en yl-2-p en ten e, b .p . 96-99° a t 22 1 mm., rip 1 .5 5 6 1 -1 .5 5 5 0 . This m aterial d ecolorized a bromine so lu tio n very r e a d ily . P reparation o f 5-ch loro-2-p h en yl-2-p en tan ol 'Ha - ch2- ch3- ch3ci In a one l i t e r three-necked f la s k f i t t e d w ith a condenser, s tir r e r and a d d itio n fu n n el was added 9 g . (0 .3 8 mole) o f magnesium. Bromo­ benzene (65 g . , 0.1*1 mole) in 200 m l. o f ether was slow ly added and the 76 s o lu tio n was reflu x ed 30 m inutes. 5 -Chloro- 2 -pentanone (38 g . , 0 .3 1 mole) in 100 m l. o f eth er was slow ly added. The so lu tio n was reflu xed one hour and then hydrolyzed w ith d ilu te hydrochloric a c id . la y er was separated and dried over potassium carbonate. The eth er A fter removal o f the so lv e n t there was obtained 52 g . (81$) o f supposedly 5 -c h lo r o - 2 p h en yl-2-p en tan ol, b .p . 100-120° a t 3 mm., n ^ 1.51*02-1.51*92. The product contained a sm all amount o f unsaturated im purity, presumably due to dehydration o f the a lc o h o l. Preparation o f l*-chloroeyelohcxanol The procedure was that of Owen and Robins. 75 l,l*-C yclohexanediol (II 4.O g . , prepared by reduction o f hydroquinone) and 300 m l. o f concentrated hydrochloric acid were placed in a 500 m l. round-bottomed f la s k and the stopper was wired on . The f la s k was heated fo r lU hours a t a temperature ranging from 80-90°. The lower la y er was sep arated , and the upper water la y er was extracted w ith chloroform . carbonate. The combined organic la y e r s were d ried over potassium A fter removal o f the chloroform there was d i s t i l l e d 70 g. (1*2$) o f l*-chlorocyclohexanol, b .p . 72-92° a t 1 ram. About 20-30$ of the o r ig in a l l,l* -cy clo h ex a n d io l could be recovered from the water la y e r . Preparation o f li-chlorocyclohexanone The procedure o f Sabetay and P alfray was used. 76 In a two l i t e r three-necked f la s k , f i t t e d with a s t ir r e r and addi­ t io n funn el there was placed 230 g . o f l*-chlorocyclohexanol. The s o lu ­ t io n was cooled and a cooled s o lu tio n con tain in g 230 g , o f sodium 77 dichrom ate, 180 m l. o f s u lfu r ic a c id , and 700 m l. of -water was added s lo w ly . The ic e bath was removed and the so lu tio n was allowed to come to room temperature w ith s t ir r in g fo r three hours. ex tra cte d w ith carbon te tr a c h lo r id e . dried ever potassium carbonate. The so lu tio n was The combined organic la y ers were A fter removal o f the so lv en t there was obtained 160 g . ( 70 $) o f li-chlorocyclohexanone, b .p . 70 - 79 ° a t 7 mm. Preparation o f Ij-chloro-l-m ethylcyclohexanol Cl To a th ree l i t e r three-necked f la s k f i t t e d w ith a condenser, s t ir r e r and a d d itio n fu n n el was added 36 g . ( 1 .5 moles) o f magnesium. Methyl io d id e (230 g . , 1 .6 m oles) in one l i t e r o f eth er was slow ly added. A fter th e r e a c tio n was com plete, 160 g. (1 .2 1 m oles) o f li-ch lo ro cy clo hexanone in 600 m l. o f eth er was slo w ly added. The so lu tio n was s tir r e d fo r one hour and then hydrolyzed w ith a saturated ammonium ch lorid e s o lu ­ t io n . The eth er la y e r was separated and the water la y er extracted w ith e th e r . The combined organic la y e r s were dried over potassium carbonate. A fter removal o f the so lv e n t and r e c r y s ta lliz a t io n from petroleum eth er there was obtained 100 g. (70$) o f h -ch loro-l-m eth ylcycloh exan ol, o m.p. 93 . A nal. C a lc 'd . fo r C7H130C1j Found: C l, 2 3 .6 , 2 3 .7 . C l, 2 3 .9 . 78 Preparation e f U -chloro-l-m ethylcyclohexene CHa Cl ii-C lilere-l-m eth ylcyclohexan ol (160 g . , 1.11 m oles) and 1 .2 g. o f io d in e were placed in a 500 m l. round-bottomed f la s k . The f la s k was heated in vacuo a t 110-120 mm. and the product-water mixture d i s t i l l e d a t approxim ately 7 5 °. The upper la y e r was separated and dried over potassium carbonate. There was obtained 123 g. (85$) o f U -ch lo ro -lo 2% m ethylcyclohexene, b .p . 88 a t li3 mm.f n^ 1.U78U. A n al. Calc*d. fo r CvH^Cls Found: C l, 2 7 .2 . C l, 2 6 .1 , 2 5 .8 . The r e a c tio n o f phenyl magnesium bromide w ith -butyrolactone Procedure A To a 500 m l. three-necked f la s k f it t e d with condenser, s tir r e r and ad d itio n fu nn el was added lU g . o f magnesium. Bromobenzene (9ii g .) in 200 m l. o f eth er was slo w ly added, the s o lu tio n was reflu xed fo r one hour and then f i l t e r e d in to an a d d itio n fu n n el. The Grignard reagent was slo w ly added to a s tir r e d s o lu tio n of h3 g . o f 300 m l. o f e th e r . -butyrolactone in A fter the rea ctio n was com plete, the mixture was hydrolyzed w ith d ilu te hydrochloric a c id . A fter removal o f the so lv en t and r e c r y s t a lliz a t io n from petroleum ether there was obtained 35 g . ®f 79 a compound, m.p. 70 . The in fra red spectrum did not show a carbonyl or hydroxyl peak. A nal. Found: C, 86.25} H, 7 .9 6 . While th ese v a lu es correspond t© C20H220 , t h is compound i s probably 1 ,1-d ip h en yltetrah yd rofu ran, C16H160 . An attempt to prepare t h is com­ pound from 1 , 1 -d ip h en y l-1,^ -b u tan ed iol (prepared below) by s tir r in g w ith hot concentrated hydrochloric a cid resu lted in a compound which when r e c r y s ta lliz e d from petroleum eth er melted a t 60-65°. A mixed m eltin g p o in t m elted a t 6 0 -6 6 °. Procedure B Bremobenzene (90 g .) in 30° nil. of ether was added to lit g. o f magnesium. A fte r the re a ctio n was com plete, the mixture was f ilt e r e d in to an ad d ition fu n n el. The Grignard reagent was slow ly added w ith vigorous s t ir r in g to 70 g . o f *¥ -butyrolactone in one l i t e r o f e th er. A fter the r e a c tio n was com plete, the mixture was hydrolyzed with 500 m l. o f 6N hydrochloric a c id . over potassium carb on ate. to stand o v ern ig h t. cyclohexane. The ether la y e r was separated and dried The ether was removed and the residue allowed The s o li d was f il t e r e d and r e c r y s ta lliz e d from There was obtained 21 g . of 1 , 1 -d ip h en y l-l,U -b u ta n ed io l, m .p. 108° ( l i t . v alu es 1 0 8 ° ) .^ From the liq u id remaining a fte r the s o lid had been removed there was obtained two g. of a s o l i d , m.p. o 68-9 . A mixed m eltin g p o in t w ith the compound prepared by Procedure A showed no d ep ressio n . 80 SUMMARY 1. Acid c h lo r id e s were shown to r ea ct with cyclopropane in the p res­ ence o f aluminum ch lo rid e to give a 60-80$ y ie ld of f t -and -ch lo ro ­ k eto n es. R -d -c i + ctt 1 0 CH2C1 R-C-C^ and R-C-CH2-CH2-CH2C1 The stru c tu re s o f th ese chloroketones were proved by dehydrohalogenation to the corresponding unsaturated or cyclopropyl ketones r e s p e c tiv e ly , and a ls o by reduction o f the unsaturated ketones to the corresponding iso p ro p y l k eto n es. M elting p o in ts and mixed m elting p o in ts of d eriva­ t iv e s and in frared sp ectra were used to e s ta b lis h the id e n tit y of the unsaturated k eto n es, cyclopropyl ketones and isop rop yl k eton es. The acid ch lo r id es used were a c e t y l, propionyl, iso b u ty r y l, n -b u tyryl, cyclopropanecarbonyl and b en zoyl. T h e ^ - a n d - c h l o r o k e t o n e s were formed in approximately a 2:1 r a t io . They could be separated by c a r e fu l fr a c tio n a tio n . In some c a s e s , s e le c ­ t iv e dehydrohalogenation o f the f t -chloroketone w ith sodium bicarbonate was p r e fe r a b le , the mixture o f isopropenyl and *Y -chloroketones then being r e a d ily separable by d i s t i l l a t i o n . This rea c tio n g iv e s a convenient method fo r the preparation o f many isop rop en yl k e to n e s. 2. li-heptanone. D icyclopropyl ketone was prepared in good y ie ld from 1,7-dichL oroThis dichloroketone was prepared both from cl -cyclopropane- carb onyl-*y-butyrolactone and from d ib u tyrolacton e, the base catalyzed 81 condensation product o f ^ - b u t y r o la c ton e, by treatment with concentrated hydrochloric a c id . The method from y -butyrolactone was very convenient. The