,—v THE ACYLATION AND ALKYLATION OF CYCLOPROPANES WITH AN APPENDIX ON THE ROLE OF STYRENE IN THE RACEMIZATION OF (I-CHLOROETHYL} BENZENE Thais for flu Dom-u of Ph. D. MICHIGAN STATE UNIVERSITY George Levitt 1957 " "i Q Ii‘f':'"*~.'\rT . . ’.'.'1 L. iii: .. -..‘..JV~.H\>I Y EAST LANSING, MICHIGAN LIBRARY Michigan Sm: University TL3.ACIL11 TICN'AL. ALIILATI 31 OF CETLC?RG A323 WITH MI APP TZILIX OBI 9-. non-Down- 0“." III-hf “a m '9‘ t fi- -n of”. .mq‘, IL’iLa 3.0114: C;i)1.;... «1.4 1.9.4 An 1 Raw; AlLdLL¢U£i A V‘T‘fi" -_-- «up; I, n ‘ CF (14-.:JU 5VLAAa¢sL-L‘ LLiai'iL'J-‘LJI 4| 11.. Lu J, George Lawitt Submitted to the School of Acbzanced Graduate Studies of Iiichigan Stata University of.Agriculture and Applied Scienca in part 41 fulfill.3nt of the requiramanta for the da J #93 of BOOTH" OF PKILSSOPHY Department of Chemistry 199' fl'fiva” 1‘3“ 1""!!! Ultzd‘JI’ILuHU IL. all» The author would like ’03 exitpress his sincere appreciation to Dr. 3. Hart for his guidance and counsel Chris-13 the cmrse of this work. He in also indebted to his parents for their financial assistance. at.» :-;:.-~'~:1- 999:9»:91991-414999 To Julia iii car-.1737 rx awn-m 4.44.1443 U? C .4. 1....»1 “ 3 ? nmwr'n ‘5b'VUVV V‘ COCOCCCOCOOOOO0.000000000‘OOOOOIOCCCOOOOOOOOCCOOQOOOOOO wmnffiomn‘i . ' ‘ ' ' . . . ' ad... iii-$3-h-0b- .OCCCOCCOOOCCOOOOCCOOOCOOIOOOOQOO0.000.000...000...... I. Eta-porimccrts Bulb; with tho I’mi‘mfiom of the Emoticonuu A. The Reaction of $09-$31 Chloride with C}'Clg:§m-rene.’.'..; B. Acctyl Cffioridc anti Alumimm Chloride with S-(ihloro- _ Z‘Pantanonao0.0000000000000000...ooooooooooccccooco C. The Reaction of Acotyl Cifloflda with Cyclopropano in the Pros-once of Added S-Chloro-2-psn‘omoneuuuu. II. The.Acylation Of substituted Cyclopropanes....o.........c...‘ A. Acetyhtion Of 1,1-L‘imethylcyclopropan8”..§..c....c.;t 15 1,1-Eimot3vlcyclopropana....................a... -gv iv C. 2,2-Bimoth31-l,3~propanediol.......o...... b. 2,Z-Eimothyl-l,3-dibromoprop&ne..o........‘ Co I’l‘PimCt.”lquleroPflneocoo-0000000000000 2. ,‘Ieopant 7' Aceta’seococoa-00000000000000000000000. 3 . me Reaction of 1,1-ll'i'not‘wlcyc10propana with Aluminum Chloride............................ h. The Reaction of 1,1-3'ioetmrlcyclopropano with Acctyl Clfloridc am! Alumintm Chlorido . . . . o . . . S . Structure Proof? of h-Chloro-3 ,h-disnctfizyl- zfial‘tarfioonaOOOOOOOOO0.00....0.000000000000COC a . Bolzalo gsmtion ' Ah zinc in acetic acid. . . b . Lobyflohalo actuation with sodium hydroxide . c . Lava. Lalo genation with sodium carbonata . d. Propamtion of h-Chloro-B ,h-dimo'tlu‘li- pmmzmo by the motion of ac ctyl 012.335.2193 with 2motlm'l-2-butana . . . o . . .5 Bo Acetyhtion of CDCClOPI‘OFyl Ciflcrme..................._ 1. Cy310?r03y1 Chlcrifieooccoo-000.00000.00.00.00.00 2. ' :19 Reaction of Acotyl Chloride with Cyclopropyl Chlorifiaocoo...coco-00.000000000000000.coco-c 3. Stmcture Proof of h-Chloro-Bmotmrl-B-bu‘m-Zy 039..0000000000oococoocccooooocco000000000000 a. Ito-Suction with lithium £31119.me mrfiride. . o " ' b. Embrogcmtion of h-chlcro-B-metfiwl—B- buien-Q-one.......o...................; 23V3CD~fl-J-J -J Ch Ch U1 U1 U1 F‘ SEEP H 5 17 2O 20 25 25 .00“. .39.. 1' OCYOCUOI'. Iboiianv’ufioflbvtn 03.00-690 QCOOO 060.0 A...OJ.‘ acoacovt-o-o - I u Ii. ‘.c 1" -09~'r'~¢Iq§;COoo Qwa.‘.¢n‘t’lo loo-Van 8. 00'.‘0.. '...‘..I.U"V-IJ .0. SD. noofiooc‘fiotO-Iii . . O I C ;..‘ b 1 c. ' f r c Q . ‘9. d . 6 a a Q £2.13 or catr'r'ms - Continued Page c. The reaction of acetyl chloride with marl Ghlorideoocococoo-cocooooocoooccccoooooc C. Acetylntion of 1,1-E-ichlorocyclopropam................ '9 1. 1,1-uicnlorooyclopropsne..o...o..o....oc........a 2. T118 Reaction of 1,1-‘Lichloroq'clopropane with ‘ 9 Aoetyi.Chloride..........o.................... D. Acetylstion 0f PhGflYlC’YClOpI‘OWlO-o00000000000000.0000. ~ 1o Propenahion 0f Phanylcyclopropnna...o.oo......... 2. The Reaction of Phezvlcyclopropane with Acetyl -=:ChIDPidOoooooococooooooooooooooooooocoo-cocoa. 3. Structm-o Proof of Myclopropylacetophemna...“ a. Oxidation to p-cyciopropylbenzoio acid...” b. Oxidation with chronic oxide............... III. Reactions of Cyciapmpano with Seven]. mes or W.... A. Chloroacetyl Chloride.o...o.o..;a....................ao 1. Chloroacotyl Chlarid‘oocooccooocoooocoooooocoocoo 2. The Reaction of Chloroaootyl Chloride cod Cycloo. propanaocoocoo-00000000000000.0000oooccooooooo 3. Proof of Structure for lucmm-B-uetlvl-B-buten- 2-03..cococoo0000000000000...0.000000000000000 ‘- Hydrogenation....o...o..................... be Reduction With Zine.oooooooocooooooooocoooo 0. Promotion of Bmflvl-S-butend-mc from butanoneooocoooooooooocooocooooooocooooo - (1. Reduction of 3-Hethy1o3-buten-2-ono with Iincooooooooooooooooocoooooooooooooooooo o. Attempted synthesis of 1,h-dichloro-3- MCfihyl‘E‘butflnOneoooococo.00000000000000 1) The preparation of P-chloroiso- butyryl Chlflrideo00000000000000... 2) The reaction of F-chloroisobutyryl chloride With diazomethane....o... h. The Synthesis of 1,5-Dic1floro-2dpentamneuan... a. 'i'he Preparation of h-chlorobutyryl chloride iron bu o3c'o'mctone............. b. The preparation of 1,5-dichloro-2-pentanone from h-clflorobutgc'yl chloride and disco- methaneooooooocoooooooooocoooooooooocooo Bo t-Butyl Chlorideoococo-00.000.000.000oooooocooooooooooo C. Sulfonyl Ciflorides with Cyclopropane................... Do‘ACthl Percnloratao0.00.00.00.00coo-00000000000000.0000 10.538t3’1.P€TCh10r2t6‘WiLh Cyclopropane.....o...o... 2. Acetyl Perc‘ 1.10er vi -.h 1,1-Lmeuu'1cyclopropane. xi 28 29 29 29 30 30 32 37 37 37 38 38 33 39 h1 h1 193 16 15 1:6 hé us 50 xo .. e n.- 'l 990 ' ‘l c I o v 0 O . o O ‘1 P g. I a - u . n“ - .‘d J .. Od‘jb J c- Q l i ' - . . f 9 § J O 0 c C O Q . «v 0 .o. ' D o o I s d I m - . . ’ 4 9 n f $ 0 ‘v V .. t a .y'OI ~ . .. l V 0:01 . c-OI‘ofiofl‘b 0 O I O " . . ~ 0‘ J ‘ C o . I i t 9 u. D... 'r‘QO-fi ".251: cocovtfiiil \ ME 01" CGJTETI‘S n- Continued Page Amea‘ Melting P0131“ find Spam-000000000000oooooooooooo n ””951”! UV” U‘ 0..OCOOCOCOCOOOOOCOOOOOO...CO...00.00.0000...0.0....00... smzmIOOOOCCOOOOCOO...OOOCOOOCOCOOOOOOOOOOOOO00......COO....00.... APPRE'ROOOOOOUOUOOCOO0.....00000.00IOOOOOOOOOOOIOOOOOOOO0..0...... rmmflcflWO‘OOOOCCOO000.......00...O...O.0.0.0.0...0.0.0.00... man::rlnm00000000OOOOOOOOOOOOO.JOOOOCOOOOOOOOOOO0.00.....0000 I‘iace‘byl W10 AnhydrideoOOooooooooooooooooooooooooooooooo Preparation of Carbon Suboxide by the Pyrolysis or Diacotyl Tartaric mwmideooooooooooooo0.000.000.0000.oooooooooooo FfllonjCC‘dg-acj-d‘dgooooooooooooooooooooooooooooooooooooooooooo acetic-da‘BCj-d'dooooooooooooooooooooooooocoooooooooooooooocoo AKCthl-da'CthrmeoQuoooooooooooooooooooooooooooooooooooooooo ACMhmnW,Q,C‘daooooooooooooooococoooooooooooooooooooooo UiiGfiQ’I-d3'bm1 ClOOhOlooooooooooooooooooooooooooooooooooo (lfithWG'Ehfi'I-Z’Z,2‘d3)banzenaoooooooooooooooooooooooooooooo (1-Chlorooflvl-2,2,2-da)banzono with Phenol in Bowman"... mmm0000.0000000000000000000000...0.000.000.0000...0.0.0.0... BRIWAPE‘XOOOOOOOO0.00.0.00...0.00......0.0000000000IOO0.0.0.0... x11 60 61 77 79 79 81 81 o s 1 8 . o 7- O . 0 -. ) .-.s_ r, z ¢ ~ A v I u v ’ . - d v . 1 4 IL . 1 a 0 .o . , - o . I. ‘ . . . .; o . . . . ‘ _ p . 0 0 v v v 0 o v - u : o o r ‘ a - - o - ~ 0 o . a ‘ )- Q a A ‘ o x t n 9 g g g , . o . ¢ . A g . . . o .l .4- v o > c .a o .2 l 9 - Q t + a I w l o - 9 O . I J ' ‘ O "‘ O -. ‘4 D f D - In I l l I Q t ‘ . . Iv 1- t — u w I s C ' C v l . I v i v a ‘ I Q h s . ' fl ' I, Q g 1 ' u ‘ . Q n . v I \ - ‘ o I u o . n o O r u b v n 9 9 q . - w I ~ . a o 1 a . . . ~ 3 . ~ H . a I . O ‘ - 0 . 1 o . . g p , o l g 2 1 ‘- I v r - a - O . . p s L | u v o 9 5 o , . r . - ; v . u o x . - | -. t n- o u - - r I . a o h. #5» I ‘ - ‘ ' .7 ' ‘ 0- ‘ - o - - ‘ o '0 o o o . N . u I ‘ c . u u o n c e 1 o a .. '7 A u N O O - U o i -’ I o ‘ an . ' 4 . 4 ‘ a a d o t A Jr - ‘ 0 x \ o I o . x o o . a a e l l .’ 'l o 6 Q o g i : r n I .q Q n ‘L ’ . o . a a‘ o r r a. i o . S O O s I Q .‘ Q . - . . o : a 1 n 1 ~. .- J o a o o a . .r ’ . -g - i " - - ~- ‘ . A u- ‘4’ ., .. . . .. . . y g .‘ g 4 .9 . c¢ - . o o o o tr t i s -: .94 Q9 r yahoo 09 ‘- CO '§'~0-.¢-"-uft'I}!tillifo'OIOI"l!‘.’§..'a.di‘v ' T132113 Page I Distillation of Product from Reaction of Cyclopropmm with t-Butyl Chloride through a 7S-cn. 001mm 0! 1" monster Packed With 1/8” 61888 15611398000000.0000.ooooooooooooooooooo 511 II Deuterium Exclmgo of cgzscgs on, (1.75 Molar) and Phenol ‘ (2015 KL01131.) in 382128116, 33 9 3’4 l‘imlthSoooootooooooooooooooo 87 xiii o" (I 0 § HGT-.3 I II III II LIST OF FIGURES hmm'3,h'dmw1'2wmm,lqu5“90000oooooooooooooono Lit-Dimatlwl-Z-pontamne, squeeze...”unnuhu'nuuu... 3,h-Dimthy1-3 mun-2 -ono and 2 ,3 ,Bdhrhmfiwlcyolobutamno from 10;: sodium hydroxide demdro‘ualogmation, 30119880000000. 3,1»? inan-B-pmtcn-Z-ono from 10% aodiun bicarbonate dWhfllOgflflBtfih, WengococooooooooolooOooooooooooocoono Curve I: 24Zeflvlhoxm-2-ono; Curr. II: h-Chloro-J-mahhfl- 34mm-2-onouuuouuuuuu.....u...uunu.uon“... .1. Q "O‘IvOIu C h-CthN-BMTUI'B-bum-ZW, Squeezflooooooooooooooooooooo Unidentified productjr on cy'clopropyl chloride with ocotyl Chhride , hop .3 626 . aqueezeoooooooooooooooocoo-000000000o h‘ChJDI'O‘an‘B'b‘XW-Q‘Ol, Cqueafieoooooooooooooooooooooo Unidmtifiad proact iron 1,1-dichlorocyc1opropono “with 30615371 01110151138, Squeezaooooooooooooooooooooooooooooooooooooo 2-Cyclopr0pyhcctophamne, 2% in urban tetrachloride , 0.05 EEOOOOOOOOOOOCOOCOOOOOCOOOOOOOOOOOOOOCIOIOOOOOOOOOOOOOOO Curve 1: g-Cyclopropylacotophmno, Curve III Acotophemono. XII Unidmtified product from phavlcyclopropona with acetyl XIII XIV IV caloridGOOOCOIOO0.00.00.00.00.0..i.......0.0.0.00.00.000.000. lfimm-B-mtlvl-B-butm-Z-one, aqueezaooooooooooooooooooon. 1,5-Lichloro-2-pentanono from cyclopropano with chlomcotyl Gill-OMB, aqgeazaoooocoooooooocoooooooooooooooooooooooooooooo 1,5 ~Dic1floro-2 «pmtanono from h-chlorobutml chloride with mmg' .qneezeoooooooooooooooooooooooooooooooooooooooo 345W1y1'3-Ntm'2-01, squeeze...ooooooooooooooooooooooooooco xiv Page 13 16 18 15 23 2h 25 27 31 3h 36 no ’5 ‘ 9 - l o ’ - 1 5 I . - v . O I ‘I o I a l v 0 ' a ‘ .. ‘ \ I O ‘ I 7 v V '0 Q ' l V 1 v v y g . ’ r... inr:. .ooal-C v i I . b a ‘ f 3 a . U ' v '. t . 1 v ' ln~tl|a rfivnlv‘fi O vocal-33‘0- O 0 O q t I 1 l‘ o O a . o . . ' n C O a _ i . an O F I z I I 0.0...” O..- ‘0‘."‘..0 owovo' Q I . l - o o t . ‘4 wtfliohofioo§ D ' 0 O I O I b b a C. I v 0 ‘ o 9 -¢ . . .— l J .- O. . ; I‘ . 6 ~ . '4._ 1.. .. .. at Il‘do LIST OF FIGURES - Continued XVII XVIII xxx Fraction A, from 9-0? :goroiso‘outywl chloride with diago- - methane, b.p.3 52.750, ecfil3ezeoooooooooooooooooooooooooooooo Wtion B, from F-oElomieobutyryl chloride with disso- m. hope: 75450. aquweoooooooooooooooooooooooooooooo Unidentified pmduct from sodium bicarbonate treatment of metiona "it" and "B", Ber-18339000000000...0000000000o.000.00 Distillation curve: temperature Y8. 3. product iron t-butyl chloride fifth Cfilopmpaneoooooooooooooooooooooooooo-ooooooo Distinction curve: refractive mm vs. 3. product from t-butfi'l chloride With CE'ClO?I‘OIIilneoooooooooooooooooooooooooo Unidentified LUCY]. chlori: 63.8 from WW1 chloride with C'flhpm bopgg‘ 55.65” ’ Squeeze-00000000000000...ooooooo Page 1:8 h? 51 55 56 58 ‘C..‘ .I“ 1 v"lh '0‘... 43359.3. 4.00.. C ‘01. '4 momma: Among the saturated cyclic hydrocarbons, cycloprogane represents the most unusual as well as the smllest ring. In fact, the cyclopropane ring behaves chemically and physically more like an olefinic double bond than like the larger saturated rings (1). Physical measurements, especially spectral data, have mpplied such significant information con- cerning the unsaturated character of cyclopropyl compounds. Ultraviolet absorption spectra show that there is confugation between a cyclopropane ring and In ad‘scent double bond (2-24). The bathochromic shift is less, however, in the cyclopropyl conjugated systems than in unsaturated ones. Recently it“: demonstrated that a. chain of conjugation is probably not transmitted through a cyclopropeme ring (5) . Infrared spectra, mainly of cyc10propyl ketones, also indicate that the conjugative effect of the cyclopropyl group is less pronounced than that of an ethylcnic bond (’x). In addition it is significant that cyclopropyl compounds exhibit C-H stretching frequencies at 3010 ch and 3090 curl, since olefins also absorb in this region (3,7). Other physical measurements such as molecular refraction (8), dipole moment (3), and electron diffraction (9) have also mpplied important data relating to the ff -bonc‘-ed character of the cyclopropane ring. ' Typical of the reactions which occur with cyclopropane paralleling those of the olefinic double bond is the addition of hydrogen halides to forte n-alkyl halides (10). Similarly, \ u ‘ .r i , t I . . y . . . . .. . , . o .‘ . D ' l . P .. . . . , . .. . o o . g I all. . I i — _ a D c . I 4 . , n p 1 n . . . . . o . . . . a .t o. . v a o u a r y » .. 1‘ I. a v a . . . i .. v . a . .. , .. . A n . . ‘ . i ‘ a l t. V . o r i i . . J . ~ p o. . . > I a . . a I V n . r , . a . \ ‘ I C a . .Ja ,. A . . t o .D l l . v . I . .I . .bl . . . . . t 4 f . ¢ . ‘ . . u .. ..A \ . ~ { . . . ., o q , o a . . u . u . III p u . I . . I . a 7 . . ~ . . a . a .V! .. r . . . h .u c V 1.. .t ‘ z . . . . v x _. .\ u r . v u h . . . . . a . . . . . . . In“ . . . \ .. . v. 4 a , r 1- (u v a I. a , . , . g . . .m. . . .— v m ’ . r 1‘ _ l p . . o, 1‘ U 1 I . _ t z ~ ~ ‘ . a r fl . ~& ~ . : , I. o J . r n a . . . o. o 1/ ,aL /C3'\ o m3]: -—-—-» ans-03,431,431- cn, —— on, organic acids in the preseme of boron triflnorids practice n-Ipropyl esters (11). Indeed Markounflzoi‘f'l rule is obeyed, since in the addition of a hydrogen halide to an alkyl abstituted oyolopmpane one obtains predominantly product in which the halogen is bound to the carbon atom holding the largest timber or alkyl peeps and the averages has added to the least mbstituted when (12). This is illustrated in the following arm-«plot cs, ens 9H3 l t c ce-cs, o mmm-cocn-ce, / I one \ / CH: cu, Thachzdisa of. KohlerandConant (12) havealsoshomthatasystacon- listing of a Moral ring attached to a carbon]. mp 18 ulnar to am-amsaturatad oarbomrl compounds. Thus cyclopropanecarboaqno acid. adds hydrogm bromide as sham. CH, - on - coon o 3-2: --o Br-CH,-CH,-CH,-cooa \ / CH. Wolopropane also adds hydrogen, bromine and iodine in a moor analogmsto ‘olei‘inic compounds. Hence the ring my be hydrogenated to prom (13) and the addition or bromine or iodine yields the correspond- ing 1.3;dihalogenopropano ilk). Chlorine reacts mainly by mbstitution to fairs cyclopropyl chloride (15). Cyclopropane also forms ”local” or ——_--“'k We complexes in a mar similar to ethylene. Thus cyclo- propane 1m mlaxes with plathnm II (15) , tetranitromethane (l7) and iodine (18). The nest striking chemical difference betmen cyclopmpene and the olefinic dmbla bond is the resistance of cyclopropane tomrd oxidizing agmta. Oscaolysis of vinylcyolopropane yields cyclopropaneoarbomldewvde and Warned. (19). and with cold aqueous potassium pec'xranganate (20) W 1. Wed to cyOIOpropyl-lfi-ethanediol. o H OH on, II, o a a t. CH. \ pans-cs, 4999‘- I pace-cs, 3:. ozonide 34- \ ;ce-cno CH- Cfis on, o (331,0 The Model Cram reaction of acyl Imlides with olefins to give mutated kotona and/or e-nelokotonoo has been discussed in detail by M (21). m products obtained from this reaction are those which "weld be predicted on the basis that the adding gulps are 3-3-0 and Cl”. 0 *‘ ‘ o o u _ 7 H H RIG-01 O R'CH-CH. C—O R-C-Cfla-CHCl-R' o R-C-CH-CH-R' The analogous reaction of acetyl chloride with cyclopropane was reported by Krapivin (22) to yield a ke'tone, 05360, finish as not characterised further. More recently, in an attempt to prepare a series of YW kstcnes, Hart and Curtis (23,210 treated a chloroform sciatica of the 1:1 complex of an acid chloride and alumnus chloride with mlw. The reaction we found to proceed moth]; at f tauperaturea {rm 430° to 0° to banish 60-803 yields of ohloroketonos. Instead of obtaining the cleared X whlorogropylketonee as the sole products, homer, there were also obtained, as the predominant prozhmte, the W115 p-chloroieopropyi kebonee. 0 /cn,, 11151, 9 . 0 on, I. H | ' RC-Cl + (fig—EH, T'fl?’ ac-ce,-ca,-cn,-01 4- ac -CH-CH3-Cl on m]: other "ferme- to e Frieda-Crafts type of reaction between mlopromo and 0 WWW compound in a patent iemed to 51mm (10) intimiohhodilcloecdthoraetionofcyelopropnneuithwcyl mummedemmcmridu nomcperimtaldetdilor indication of the mun-o of the product was given. Ituithepzrpouotthopreemtinveetigetiontommimtheecope e: the mum and mum of cyclopromne. In mm, the inflame of selected mbetitucnte in the cyclopromne ring and in the misting or alkylnting agent in determining the course or the reaction unlined.r1t1mhapedfintinthiaw(£ormle,byet:dying thodirootimofring-opuin‘ofcmbetimtedcyclopropcm) napoleon weldboobtuinedtothonecheninorthemmlrmmtdu- covered Iv Guru! (21;). 5,; ..r b I . s s q , u . . , _ . c . _ . 3‘ .. . A I‘ ‘II ‘ ”r p . v, . . . . i ‘I n I v I. . . v . z A » t I ‘ . 9 . / . ,. . _ . w 4‘ v. V. r .o. . . . . o . \ c _. . V. ~ . . . A! 4 . . . r a n t. 1. . a 'C r i l . . . o l v . . u . c . . a A r. .. I o a . .I . i . . . . . on: m1hcfig~fiym AA“ (dubq'b' L4. I“ I. WW Dealing with the I-iecrumism of the Reaction A. The Reaction of A0331}. Chloride with Cycloggogege: ' The tolloflng ruction was carried out according to the procedure described by Curtis (2h). This on. periment ms repeated BM'e.a-.1 time in order to deterrdine the average yield. In a two-liter time-necked flask, oqnizlpod with an addition bdrm-cl, thermometer, blow-out mnemoter md rmbore stirrer, there ta: placed 133 a. (1 mid) of alummm chloride Add lOOO ml. of chloroform. The mixture was cooled to 0-50 in an ice both, end 78 ‘3‘ (lmle) of acetyl chloride we add-ed chlring fifteen urinates. The mixture m stirred until all of the aluminum chloride dissolved. The oddition fimnel was replaced with a fritteidtip gas delivery tube end 145 g. (1.1 moles) of cyclopmpane was slowly passed into the oolntion 3t such I rate that the preeeure in the reaction vase-31 Wmaac an. Wood the tmnperature Wham 20°. um- an of the cycloproznne had been added the solution one stirred foromhour, thonpouredintoendxhneof'lso g. oforookediceand 150 gal. of oomohtnted hydrochloric acid. The chloroforn layer was equated, inched once with 500 ml. of later, once with 500 ml. of 10¢: Indium bicarbomto. and afiin with 530 ml. of Inter. The chloroform colution m then dried over calcium chloride at 0°. The solvent was rumored a m the pot tw’peretame being kept below hOo. There was . ‘- ‘ ’.‘ a '1 v ’ "w ' ‘ ~1 ‘_ _' _ ' . 7' - . w, I .' ‘- O 1 I n V _ ‘. V - . . m _ t . 4 »' 1‘ _ ~ ‘ F. . A\-.<' Eu-.. — ' ‘ > ‘3 i L ‘ V .. '. o ' ’7 . v v V ‘ l ‘ ‘ 1 " . 6 ~ ‘ “ ’ ' ‘ I . . J ‘ a .. A .- 7 I 7 q u "a V‘ o ‘ ' -.. A I 3 q .I ‘ I t .. 5 1 . . i ’ _ ~ .7 v \ ' u “ « c ' ' my . --. - -‘ .‘ u . _ . ’ . .' n. ‘ - v v. f " ' ‘ I W ‘ A ‘ . " \ A " .J i . I .- l ‘. u r l ' q . _ . l . ‘ l " “ c l v z . ‘2 A ' ’4 ‘ , 0 : u .‘ I. l r A v V V- i. 4 w. ' -- ‘ . . ., . "" ~ ! > " _ ¢ - o .4 1 ‘7 ‘ |'v p ' V ' ‘ ' G. a ' l .(u .1.-‘ .m- «'I' ' l v ‘ l .7; . .; . ‘ . , - ' "7" 7 r ‘ M} . : ' u ' . _. . ’ .o O. i I I ' k n» r ’ ‘ - . '. I _ ‘ . - x ‘ .‘ ‘ . . . > _ a a ’ " . . u . 3, 7 'K . A I v . o 7‘ _> ‘ I 4‘ obtained 30-33 g. (25-23;) or semi-demons t.p... ass-75°, n30 Lissa-mm (lit. values, hp.” 70-72", 213° 1.1071 (214)). The mterial collected in the dry ice trap in the preceding distillation mariodovaotusilmomomto. Odo mummonomodded and there as distilled 25-27 a. (31-33%) a: Bacthyl-B-buten-Z-one, 3.13.; “no 95-100", ago 1.15225 (lit. values, 5.1).,“ 98°, 1125 l.n229 D (21%)). B. Acetfl Chloride and AM” gfimg vim fi-cm $m‘me minty groans (0.25 mold) or SM an added to c chlmtcru solution containing 78 g. (l solo) of acetyl chloride and 67 g. (1 mold) or dmnim chloride mod n dW’ is the wood!- ingocpcimmt. its solutions” stirrcdtorcnohun-ct o-lo°and worked up as previously described. After rmnl or the chloroform colvcnt there no moved-ed 21. g. (80%) of S-chloro-Q-pcntnnom, b.p... (id-72°. No J-nathyl-B-butai-E-onc nu obtained. _ Rotation of Acct 1 Chlcgidc with gzclome 1n theirgccmtg Added -(3 oro mtamono ' rho deflation m cord-d out exactly as previously described, arc-pt this ho z. (0.38 solo) or 38 z. (0.31 nolo) of 5-chloro-20 Momma Justpriortopessmgmthocyolompue. Their. on W 21:41 3; (31-3355) or summi-B-bum-e-m. mm at... 96.100'; no um want or S-ohloro-2-pmtanonc obtained u 70 g. inthoflratcxpcdnmtcndfi a. lathe second. Anal-133nm. mowed-1 of tho addod S-cth-Q-pmtanone, the yield: or can music! we 33 z. and 26 g. respectively. 0. l' II. The Acylaticn or Blbfiitutod Cyclopropmes low one A . Acet‘rlation of oDiMffimd- l. 1,1-Dimfivlcyclomozme ‘53» lie-4:1»: .4“: - canoe or, This compound was prepared by the procedure described by 23111th 5:. 5;... (25) as modified by ohm-triage $3.». a. (2.5). In a three-liter flask fitted with a reflux cal-denser, stirrer and n one-liter dropping mime-:1, there we placed a solution of 150 g. (3.5 moles) of sodium hydroxide in 750ml. 01‘ 95,1 otlmnol. A collation no prepared froze 5’00 ml. of 36,1; fomliiewde, 130 g. (2.5 moles) of isobutymldohy'de‘,‘ and enough ethanol to give a homgenema solution. The latter collltiori in: added dropwlac to the etl-ianolic alkali with stirring. Trio solution was tarmd to reflux for 214 hours and then W on c Item bath, at mtcr aspirator pressure of about 20 non. of mommy, to rmo the lover boiling componmts. The residue was mimtod fitb oigit ISO-oil. portions of other, the other cortractc confilined enu after removal or solvent there we distilled 11.5 g. (56:5) of 2,2-dimetm'l-lfio propunodiol,lb.p.1 titan. ISO-200° (lit value, 13.9.7“, 200°). In several m. it was found advantageous to distil at roducod pressure, 13.13.; layout)". Attai- recrystallization from c ominous-petrolm other mitturo the product melted at 223-133" (m value, 130° 23)). bring the course of this twostiggtion this compound was rude available oomarciafly by the Tam-assoc Eastmn Comma? in a gra'l-s of 96;! purity. Both synthetic and comm-cm mistrial was used in the mp1.» ticn described below. C ‘ C ‘1'!in compound as preyarad by tho mm of Whitmro g; .3... (25) a modified by Midge £393. (26). Foui Inmdrod m! oixtaon gram (In!) moles) of 2,2-dimthy1-lfio mafia]. m 'placod in a two-liter three-necked flask emlippe-d with n reflux con-flower, a one-litter adc'ition hmnol, a stirrer with a large Teflon paddlo and a thmometzr. A variable speed stirring mtor capable of stirring I. heavy man was used. The flask and contents were heated to 70° ond 1031; g. (11.0 moles) of phosphorous tribromifie mo aided at no): a at. u to mintain the temperature at 70°. As soon on the nixturo boom. nobilo flirting was commenced. When all of tho bromide hadboenuddodthonizhn'ommmod to 340-1500 and maintained at that mm for thirty hours. After six how: a bright crimson precipitate {mod which maul]: became: quite tarry and heavy, mixing the mixture «mm-m t6 «iv. The mixture was m'dromod by a slow dropwioa oddition’or Inter and subjected to steam distillation until tho distil- hto came on: clear. The layers of the distillate were counted: the . i O . r 1 a _, . . ‘ h ‘ o ‘ o u , ' ‘ . u a _ - l . o I t v ' l '» u ’ ’ 9 avatar layer moi-19d with etf‘m' and tho con‘sinod organic Errors driod over calcium chloride. After rmoml of tho othor, 330 g. (361') of 2,2- dimbhyi-J.,3-dibrooopm;mo was distilled, b.p.a 68-7-0", r150 1.50m. 1.5050 (lit. values, 12.1.).9 68", n? 1.3050 (25)). The desired product my not obtained in several attempts undoi- differed. cordit‘im. Thus whim the reaction . flame me allot-dad to Itond for six day! without boating, and worked up in the mm mmnr a: dmibed show there was obtained from 101; g. of the dial 55 g. of a mdnct b.p.. 75-75", age 1.1;?5‘0. This product was similar to that obtained Ihm the reaction was quenched after the addition of the reagents a 70°. Shortridgo (25) states the reaction is woodlato at 70°. Tho addition of bromine to 3 mm of phosphorous and the dioi, gt 70°, row by thirty hours at inc-.150", did not produce a steam moi. Mot. , o . «at: ‘ 3' ‘1 dogs lo 3:31”; CH CH 3\c/‘ 8 1'7/ \ 7' . 3 04.3 . Thin 0mm we prepared by tho wooednre described by Shortrifigo an. for obtaining I product of high parity (25). In I Ono-liter time-necked flask equipped with on adat‘iition funnel, moon's our”? mid reflux curb-longer comoctod to a dry ion trap, wore phood 150 :1. o: 95% otbdnol, 95 ml. 1: distill-3d vat-er and 311: a. (1.3 39101) of 11m mot. The mixture mo otirrod vigorously to provmt 17) the zinc from fuming lumps and heat we applied to 03:13 3 a 33:1. tie reflux. 'hto hundred and fifty gel-1:; (1.1 miles) of '3,’.’-3’ -t‘:-.-‘;1-1,3- dibroaopropano we: aimed di-o 31:15:) at tile txxpmture. The heating em: stirrill g were maintained for Eh hours. After 2' hours the mter me drained from the condenser jacket and t‘le mixture ms kept 1mm for 30 unite! ln order to drive over my remaining mfirocarbon. 3:13 crude mwmtaammwufihmemmrmdfimdwwcdflmoflmfim mo product (70 5., 912:) was 63.3133... e23 below 23°, 1350 “5.3 ' ”5 (lit. values, b.p..,.. 20.63, ago 1.3658 (23)). In In “mt to prepare Lineman-“larcloprogzmo by another pro- oodm‘o, mopqxtyl acetate (the preparation of billion is given imadieteh below) in py'rolyaod by cultmmlon fimgb a. Vyoor tube packed with Pm helices and untamed at tarlpemmre: from use" to 7C"-..~° . In all. cases the neoperrtyl acetate mo recovered and" raised. 2. Heep--.t; 1 Ace hate on. o ‘ u 033 --c -»c;-'i,,--o---c--cu3 0:13 This other In! prepared from neopen tyl alcohol (proper “:1 by the mtlnd of Conant, tiebb and 219mm (27)) made. ceLyl chlorhie. To 31 g. (0.35 mole) of neopentyl alcorcl wee £16.le drapwise, at 0°, 27.5 g. (0.35 mole) of wotyl chloride The .- filers was allowed to rm to road tel-.lpemturo with occasional stirring and weed to 53° for one-I'lllf hair. .ty Wtero of 3.0% sod’rllm blurb-alum was eel. 4ed drops—i: o to We any m testy]. chloride. The layers were separated and th- ‘in h!!! fished with weir-we]. 6.139.211 portions (25 to 50 m1.) of “he. “Endorphin layer: were combined, dried and distilled thrcugl In 8". Vim m to yield 25' g. (sz3) of the desired ester, b.p.1 atn. lei-125°, if," 1.39364.39L2 (lit. valuee, 13.12.... 1233-126", n30 1.3893 (25)). - ‘ 3. The Reaction of 1.1-Dinetlvlqmleprolnne with Alumimm Chloride . to I W or 26.6 g. (0.2 mole) of ellmimm clflnride in 100 :1. a: W n 0° m added drop-nee 10 3. (0.12.2 mole) of 1,141- mm. the taxation mbcture gliakly bacme yellow and “What”. Artumehourthanixturomhydrolyzedby tho medallion at later. The m we connected to 3 enter mm n dry ice trap and some materiel'm distilled into the tap gym... Distillation of the material in the trap indicated the m o! flirting ataxia). er m walnut boiling below 59°. The Miamintboflm‘naaeperatedmddried overcalcm we AM m1 of the solvent there mined n residue of 9 g. «WWMcmmtbodiatmod, «unetJm. m. m mm. This mterinl m not investigated h. The new... or 1,1-Disne‘eé'zy1c'ycloproznne with Acetyl Chloride - ad “-1. Chloride In dean-liter threemccked flask equipped with e Trubore stirrer, film‘tu, dry ice refine: condenser and addition Mme]. were placed 256 g. (2 moles) of clay-limo chloride and 1300 ml. of chloroform. Toe mixture In. cooled to 0-550 and 156 g. (2 moles) of acetyl chloride was edded nicely with stirring. The mixture mo allowed to stand for two bars, than filtm‘cd with suction into a. two-liter flask «flipped like the tint flank and cooled to zero. To the chloroform solution there was added 100 g. (1.10 mice) or l,lrdinet}wlcyclcprcpene at such a rate that the temperature remained below 10°. 8m moi-age: chloride was evolved during the addition, but this diminished after the addition we completed. The reaction mixtm‘e 138 showed to stand for one hour, and than hydrolyzed by pouring into n slurry of 1500 g. of ice and 300 ml. or concentrated hydrochloric acid. filo chloroform layer was separated, washed successively with 5’00 ml. 01' tutor, 500 ml. of 10% sodium bicarbonate and 500 m1. of tutor, and dried 07c calcinl chloride. The chloroform me reamed by distilling in w and 108 3. of crude product b.p.3 h0-70° was obtained. This we rcdiltfllcd, using c 25 cm. 091mm packed with glass helices to yield 91 g. (149%) o: h-chlcrc-3,h-dl'nethyl-2-pontanonc b.p., 1.24-2.9°, ago 1.1098.le (lit. values, mp.“- 60-61;), an 1.1;th (29)). The first motion! Md cone unsaturated product present as indicated by a week oblorption at 1615 ”.1 in the infrared (rig. I). m. Cclc'd for 07313001: 01, 23.8. new. 01, 22.8, 23.0, 22.6. Tho 2,41. dinitrcphcxwlhydrazmc we prepared according to the method of Johnson (30) end otter recryctellization from methanol melted at 130.5- 131°. 5 , i o V. u v o I b i n . A, e . . . J . . . . ‘ . . 4 c I \ i _ A . n .o .. ._ .r \ . . u . I f o l c i n . . , .6. . , . . . r. d 4 z ., . o . I . . L o . w 70 . u d A 1 c i \Q ‘ A e. . . i . , .. c ‘ _ . . i . . . . . .V o. .I e . f . x .p..‘ . q . . . w a v. . a ~ . p A ii A .. 4 U . . K. . . u . c . .' .. . _ k N , A .i L 1 u. f . . In. . . . . , . v p} u A . o . , l , . V V x . . . n i v . ‘. u ‘1 _ . . . v . . . d o J: t l . .9 u . . f . no . . .. , .4 i y o i v . . 4 . , : _ . n n .. . . .. . . . .U . n . .. IV .. o . — . . . . . . . n a a W , . .. .Q . ‘ ,3 ... . t ‘ ‘ v . , . .. .. o . c , . . ., . . e . , . n o q f fl ‘ L i , .v _. .V _ i, J i ‘ i ‘ . . .- . . r O . . . . . , v . I o n . .. ... . . 1* f . .- .A . ‘ . i . .. 7 . . I.) . q 7 l . . . l or . \G . .w . , . . . . I . n \ ‘ u A n i - _ e . A | ~ . . o D. I . d ' . .~ . r _ 1 e ‘ o . . . n . . , . r _ o o . . . I . v . , . . u, 4 . d 5 , u. . l y . i ‘ . a l. V . v I r o _ . . . o O t p ‘ . .. . . o . n a . ‘ ._ . a. a r . .. . _ . _ . n w .r . H ‘ c c b 3 .. v . a . ‘ A o h . ‘u . A w . . V... .6 . P . . , . . ,. . . .. .— . o I A n f. . t r _. ‘l . , ‘ V . v - , )I. v , , . 4 0 do , 2. . . n U.‘ l H . a... . .. 1 AR. .7 . . . . I i. . a .. . w . o .0 o . d t .- .. , . I 1.; l. to _, . . ‘ ‘ . . n u . U i . _ . . r / . 0 1 . . l a v, a . .. . i 4 . I , o i, .x h . 13 AT 20v rozunoumu 0mm 00» 02. 000 Onm 00m 00m 000. CON. 003 com. 00m. OOON OOmN Coon ooovooon q q o _ _ _ o q . _ _ i _ _ e o _ _ _ _ _i fiddl_l_fil o _ _ m” j ”0.. ...m.0 .4 . iwo no.0 iud 10.0 mmoosvm «moocmpcoglmuahnmeHolnqmsopoagolq BONVBUOSBV 4......- Colc'd. for cun,,o,.t,01x 0, 2.7.50; H, 5.22, N, 17.03. Found: C, 117.50; H, 5.271 I, 11.21. Several attemts to prepare the oeuicarbazone, using the procedure of SW and Fuses (31), failed to give a solid derivative. In addition to the diotilanlo ketone there as obtained 33 a. of a polymeric Iatsrhl not unlike that obtained from 1,1—dimetm'lcyolov- Winn! alum chloride in chloroform. When the reaction we carried out at c-Sooand ~15° the yield of the desired ke‘tone was con- siderably reduced (5.3 and 2075) and more of the polymeric mterial as obtained. ittaupts to recover unreec ted 1,1-dideefi1ylcyc1opropeno or any low boiling roarrangeumit product were rude by reducing the pressure in the systm throogh a dry ice trap to a tater aepirator. These experi- ments showed that all of the 1,1-diimtiiylcyclopropana ms converted to either the desired product, or the previously mentioned {101311191 1c material. 5. 3mm Frost 01' h-Chloro-B ,1-dinoom-2-oontomm \“ .q‘ 1 1.0 'o “tion the oeticec To a vigorously stirred suspension of 15 a. (0.2.3 mole) of zinc in 60 ml. of acetic acid and 30 m1. of water there we added 12 g. (0. 081 .151.) o: h-chloro-3,b-diznot}r{l-2-ponoenono. .no mixture was mod to gentlcroimtorthreehours, afterwhichtimetheliquidmpoured into 50 (.“of ice {and attracted with three 25-111. portions 01‘ ethyl other. on examined other «tract ‘Ifll neutralized by stirring with a potassiu Wt. solutim to which additional solid potaeeim carbonate no added until soolution of carbon dioxide ceased. The other we decanted . e . - - ‘ I ' . r I -; o ' u o . 1" , . . e '7 ... ‘ 1 c Q "‘ I . - . _ p a- ' f' 1 , i . . 1 ‘ f I 5 '. l 1 ‘1 n , v , s ,. ., '1 . ‘ u " I‘ 1 u .' ‘ . I ,1 .. - - . , v '1 4 ' " i f , IL ‘. . our 'l“ ' | 4 r-- ‘1. .' ' 4 1 . 1.- . ‘7 _,_ va' 1 -- ta__4 . .. 0~. .‘ ~' . u . ‘ I' . I 1 ‘ O A ' o I\ . - ‘ ‘ - " ‘ o 1 1 1 m n C l . . _ 7 1 u v t O 1 . ’ Q . . - g 9 7 .7 :_ . t ' ‘ ‘ I n' v. ‘ , . t _ I >. ' ‘ '- n _ . O c. . .3 V: ‘5 e I. 7 , . f 1 n— ' .4 ‘ v .. f . . I . .h 0- ‘l -“. g n - . ‘1 . ‘ 4 r u , A . ...... 7 .-. __ J» \ . . .. ,. .1 , _ . ' . _ . - -. , . 1 ~ - ‘ . D \ . p. . a 3 V . ‘ 3 3 . s I-vac .l l A ‘ . . J a. . 1 .. —' . t . . v - - . --. f f ‘ ., ‘,. ". ' - v - b '. ‘ — ‘- ~ ' I < . ‘\ l ' ‘ 1‘ . — _ , . e I 1 G \ v A _ , . - .A - ‘- . ‘ . -. v I . ‘ p , - . . - -. . s .. _ 7 . I. ‘ .. 1 . J 1 ‘1‘ a and dried over potaeeizm carbonate. After mmal of the ether there we obtained 5.33 3. (6323) 0:3;11-dhnat’r‘31-2-13mtanone, ‘14).x eta. n5-m°, n§° 1.1.193 (111.. values, 1.1).... 333-136°, 1119‘ 1.2.1232 (23)). The inirered abeorption epoctrmn of this material is ohm in figure II. The amicarbazone we prepared according to the netted of Shriner and Moon (31) and after recrystallization fronS 3:3 eohanol nelted at m~m° (1111. nine, 113-11)? (29)). b. ' t with 336.111!!! - 3‘8 Fiftem pane (0.1 hole) of h-chloro~3,hozuaow¢m one 02. or.» con Ono com com 000. cow. ooe. com. 000. ooom .003 009... 0030000 . _ _ . q ..____qfiq-__._._4d.:::d_ W. 1 _ Ltd .No 1 0.0 mummeem . 0:05:31 mlahnpmsamnnu m SONVBHOSBV 17 It 1?9-130°3 however, a. large ext-pie (2 3.) we prepared and 115m mam remrtallieatione from 505:: ethanol melted at 191-192°. All 01‘ these melting points have been recorded in the liixn'ottme (23,311, 33,36) and were attributed to the proeonce of small amounts of 3 ,h-r'..i~ motivlfl-pmtonQ-one (29) rather than a cyclobutanone derivative. , ' new“ m (0.087 pole) or h-cmnm-s,L-dmenm-2-penumm on when 200 :1. a: 10% sodium carbonate for two honre. The product, 3,h;dinet‘wl-}1-pmten-2-one, b.p.1 w" 11.5-11.9", ago 1.111152. 1.111156. no ieohted using the ewe procedure as described in the preceding experiment. n1. inn‘ared absorption :5me (fig. 117) or the product obtained from thin reaction was identical to that of the predict from the preceding reaction except for the absence of the strong m at 1780 01:1 and a weaker pm}: 1037 can“. A cyclobntanone product in less, likely to be tamed here due to the decreased nctivity of the base need. ‘ The Imicarbazone derivative we prepared and after several ”mom fm 50% ethanol melted at 191-192". This precinct did not depres- the melting point of the nemicarbanone from the preceding 2 d. _' we- etio of 2 111mm»2 Eo-dimotbvl-Z ,1 .tenone b p e “' - - t o of Aerator Chic-rife With eéic'?‘.?1;.r;- JJ'B'tg'ne A chloroforn solution of altmimm chloride and acetyl chloride one prepared in the cane manner as that use-d previously, once-pt that one .010 Li . .‘.\ p. I u 3 e A . . . .- - - - ‘. , .. ' I' «A 4 l ‘ .- , . r l - " I, '7' > I \. u "4 . ‘i V e)- . , -- I -i , , A . . . u 1. . ‘ FT . - v ' ‘ ' e m. a. i‘ - -. . -‘ O .~ . ‘ ,7 . _,‘ ‘ . a V e . 5 ‘ 1 . - '. v i e- < ~‘ .g ., e ‘ IP~ 1 .7 ~ ' ~- .. e . . ‘ . . _ . - .. -. ' . no . A A . . ’ e . L _ . _ 44 ‘1 . I . .. . ~ . u L _ . 5 i r . v ‘ ‘ « v . - .- 5 —-' ' ‘ ‘ - ' "—' -‘ -—-- x - u ‘ “" b ‘ . o .o. ' r .m - ' ,4 . u ‘ . e , y _ - . ’ . ,. . ' ' . , . - . . I ‘ ‘ ' V e- f'_ - 3. , < e ' . . ‘ . . . -, : ~ ' - o ' - . A . . we .‘ ~ - e v - , o ,. . h ‘ '1 " ' ~ ‘ ‘ ‘- ‘ J‘ ‘ . ‘ a A . — ‘ . O . ‘ f - l,’ . fi . ' - e - r g - . ‘. J I ‘- . - ' . - A ' ' .. ' J ‘ ’ ’ ~ . u ' A - fi ‘ ‘ u ' I'v ‘ u - § I, — I . . . e, , , . , .. .- . r . . , : ‘ , - . ‘ ‘ I \ " .~ '“ i ~ . _v e - - l . . - 4 ' ‘, . , , - . - ‘ S ' ‘1 p 7 Q . ‘ _ , . ' . . ~ . ' , ‘.‘ V 0‘ . ‘ 4 “ . .- , . - !- 1 ‘ - . . - 1 . . . i r i , . a , V . .- ro . . _, - - I r ‘17 A - A' _ P .9 ' - . _ . . . ‘ - .' 9 e . . . ._.'. ._ '.' ' _ ' _ x .4 . .. u I" h. ‘ .- ' n ’A .v . . ~' ‘ - . , ,, . 1’ . - e ~ ‘ ' k .' w . l . i. , I . r I i ' r4. . _ . on _ . r! . - ' - . - 5 ' ‘ . H _. . . , . 4 _. .... .' , . W. . , . - _ ~ - 1 I -— --- .. - e . e . 4 q. - . -- - .4 l ' - v _ y _. ‘ ’1 q‘ ' Y ' ' ‘ t V '1 I' '. ' ‘ . .‘ . ' v '7 ’_ . ‘ i. . h ‘ \ l A '4 o. e ' e I ‘ - r a ‘ "~ I - ‘.“. . r 1- . g- r . . . ‘ v e' w‘- b ' "1-; "‘ . v- a.3 is. bPr . e V t r . '. ‘ . . ‘ .. U ' . : r , " - A mm. 1 .’ A A . . ., . e . q . .e . . . . . . 7 . t , . . . whr‘. - .. - . 3 ... . r . 1““ 7‘ .A ,. , 18 $-30. >ozu30u¢m one o2. one can 03 com 0889, 8m. 3: 08. 8o. 88 88 83 8988 q _ _ _ q q - __~__—_ q —fiAJ¢.______::ufiuw_ W L 4'6 4 .«d 0335a eucapdnowoaenongnou mag 3363 no.” son.“ 6.0 ecogsnoaohoagefihpnm. m e. N 93 econ ~13».ng mtdbfimfinuze m HH 233 03 co» on» can one com one. 89 com. 8e. 08. 8o. 88 83 So» oooe 83 % fl 4 d e _ fi~q_____ ddq__u__—qq_:_:__q_ ._ ed 1 ed . No L 3025» 3033033353 6.0 3.309.339. sauce uoa Bonn decelmlnepnoat thhfiwfianze m B 0.3me 3ONVBUOSBV of each reamt has used in 5'30 r72 .. of chloroform. To the solution cooled to 420° 1:.‘-1 1am was aided (1113:1113. 3.9 70 g. (1.0 mle) of 241et3v1-2- butane, (Phillipa Tech. genie (9-5;: min.» 1:13.321 Laid ham fr: 1.33m? .13. tt'irougjl a 100-031. cont-1n containing 31.1133 11 31.1.0?S, 11.19.; new 3'3 139° (lit. value, 13.13., 50 33.110). Tao mention nbztzu‘e "e stirmd at - o to-e H00 for one hour and 12mm (3 ‘cmrmeel by pouring into a. SEW“; of 753 g. of ice and 150 ml. concentrated hydrochloric acid. The organic layer no mod moccasiv 9hr with 530 ml. of vat-3r, 500 ml. of 1-3;: 906 LL11 bicarbonate and (.500 ml. of rut-er, dried over calcimn cI'LlorizIe and the eolvsmt strippedo L1 vsc‘. ______. no product, 90 g. (53:), we dis-- tilled, b.p.3 116-1190 , r130 1.111400. The residue m: a poly-writ: material similar 1. that obtained from the amlogms reaction with 1,1«eeeehy1- WOIOPNMo The infrared absorption spectrum was the same as that of the h-vothrO-B ,h-dineethylé wmone from 1,1-dinethy'icycloprormzo and acetyl chloride. The 2.11-dini‘trophenyl‘vdmzcne dorimtive was prepared and after mural recrystallization!!! from not?» .1101 melted at 130.1310 . A mixed melting pom determination with the s: .110 derivative as previously prepared fro: the reaction pro-duct of 1,1-dmre..ylcyclopropane and acetyl chloride ave no depreeeion. The chloroketone obteined from this W, when dehydrohologomted as previously described, move 1 2,h-dinitrophemltvdmzone and a. somicmrbazone which were idmtical to those obtained from the some moodure with the ocetyhtion product of 1,1-dinw1yieyeleprepene as shown by mixed melting point detmmtion. 23 The chloroketone as also redacted by zinc and acetic acid to yield a product \thich m a comicarbaeone identical to that described earlier a m by a mixed melting point deteneination. B. fice'tvletion of 1131111011111 Chloride l. Cyclcpropyl chloride ca, \ 03—01 m. mound In. pmpared by the method deecrdbed by Roberts and Dir-1.1m (37) :- Iodified by Slabey (38). Cyclnpropane and chlorine no nixed an! plead throng: a aid which we irradiated by two Kan-Rad I. S. 275 In: W. Three rumored and seventy mm (8.8 30193) or W as W during eight hours of photolysis to yield 267 u. 0.0:) or Workman, b.p.1 mm. 10.5", of? 1.1.080 (111. when. ban-u. 106°, 11:5 1.11079) (33). The apparatus and detailed We and, for thin preperation were described by J. M. Sandri (39). 2. The Reaction of Acetyl Clflorifle with Cyclopropyl Chloride A caution of two 1.1m ei’ chloroform, 265 t. (2 moles) of alanine- m all 200, c. (2.2 ulna) of acetyl chloride in. prepared at min-1y W for the motion of acetyl chloride with 076W- bo um II filtered with section into a time—liter three-necked flask, Ihich in: than oqxipped with a stirrer, reflux condenser and cal-1.“... AI . L .. l r I . p ,. s. o .. . . ..~ . o I, . I . . 2.4 \l . 4 . | D . I .. o . . . .¢ ... u . o. A ‘ ~ . t l i . I. . w h 0 . . i. ' I A . O _ o u . w . fl a . . . 1 O _ .. . .. u; 21 addition flannel. Ono hmldred and fifty-whee grade (2 moles) of cyclo- propyl chloride was added mouse at man temeraturc. 'l'he temper-coin menu: rose to 35" after one to too hours. The solution was stirred for eighteen: hours, and the: poured into 1500 g. or ice. " Tho chloroform layer was separated from the amber aqueous layer and ihc hour mi attracted with five 100-1111. portions of chloroform. Even Do, the ‘1." Mind dark axiom. The chloroform extracts were cozdainod, hand mama; Iith 500 ml. of outer and dried over calcium chloride. AMMofficmfomgwanattemptmmdeto distill the promos (202 g.) at 3 m. mommy but decomposition appeared to take place. the Met was therefore added to 500 ml. or 10% sodium bi- carbonate and refluxed with vigorous stirring for two hzmra. The mixture In! cooled and the orgnic layer comrated from the brown aqueous layer. “rho moons liver was extracted with other and the other portions combined filth the orpnic layer. The water solution we evaporated and the midna W with ieoprooyl alcohol. Some of the colored material was taken up" in the alcohol, but men the alcohol was decanted and distilled Wanemt oftarryrccidnorcminod. -m'mei- «we no dried over ammonium sulfate and after removal or on new mac. vac W 63 g. (23%) o: h-chloro-B-nouvl-B- Mend-one, b.p., 32-36°, 251.1.691141. 701.. The assignment or the above m lac band on elemental analysis, ultraviolet absorption W, the infrared absorption spectrum and the retire or the products from ”rural reactions of the compound. o . .u i. l l. _ .. . l . .9 . 7* l . a . . I “m. \ . . .. l . .. ... l . 1. ca . I .c ._v ‘ v P. . v V. . .. \ . .. . . c .l . 4 .r w t c v . v o .. o C c . . v“ 1. o. 4 . . , so. 7 d . . c A . c. . . v ' .. c l l . ) n I l . v yr .. , s . c . o. o . . . . - . . ; g : l , . i l . .. I ‘ O « , u r O o . ,. c . , o l . . . . .o I . iv h . . ' . .. . \ r1 c o . . a o. a - o . . . . . t \I‘ s. o . . . w v 0 r . . . Jo. L .. . 4 . . . . . I o . a r .v. . . 3. . .1 . o I . Q . l J I I r .c n . 'Q I 1 . f . l . . a r I. v . . — . . r I V . o C f0 R) m. Calc'd. for 0532,5- Cl: Cl, 23.9 Fund: Cl, 29.3., 23.8. The 111 .mviolot absorp+ .1911 s: it; .121 (AU. V) 0;. this compound 5:onst 0. )mx. at 23); on, E 1790 wish is emactarmtic of of «substimtod a,F-unoaturatod katonoo (140 ). The im’lwed absorption Spectrum (fig. VI) chm-Jo: ttrong pm: at 15137 cm."1 and 1613 cm.-1, clmractmliotio of @9me ketonoa and a strong peak at 822 elm-1, in the region clmctcristic of trimbotihzted otl'rylonoo (32) . The 2,14-dinitrophom'l- hydrazoho as prepared and £1.ch roorwtlllization from ethyl acetate malted at act-205°. 1.11:1 . Calo'd. for CHI: 119421.81: C, 1.21.233 H, 3.721 Cl, 11.573 ' 1:, 13.73. Fonmds C, 11.1.13; 21,3.721 01, 11.951 2!, 13.330. Tho aomicarbaoono was prepared and aft-3r recrystallization from 507. ethanol molt-ad at 1314.315". _._r_1__ . Calo'd. for cg. 1021:1301 c, 111.02.: 2:, 5.71;: H, 23.93. mm: C, 110.71; K, 5.93; 1:, 211.52.. Thom we also obtainod 9.2 g. of 3:211th wteuial 11.11.; 62-650 , 21:5 1.1.1760. Tho influx-ed absorption opoctnm (fig. VII) of this malarial mo pmko at 1615 emf-1 8.11:1 1585 cm. , indicating the presemco of an a,“ mounted ketono, and 1-333 cmfl and 1725 cm.”1 1615.021 could be due o. on We at} non-co:13~.1,,oooc, mocouotcd kotono (32). Tho mbcturo could hot bow Icpuntod by elimination through a 25-cm. comm packed with glass helices. Prolongm booting caused some decomposition of this mtarm. N O '1 4-.- . . 23 9n OOn omN 0mm Ohm 8N b onswwm 1 5023ng onm ovu onN CNN q q q q d 4 .Hcooooo mmm no kudos visa x om.: «occlmlcopon Anglos. mucocdsé .HH 255 .Hoodnvo mmm ca ndHoE OH x.mo.m «occlmlooxosahnpmzwws «H mbhoo + u 0. ON On 0? on 00 ON 00 Om oo. NOISSIWSNVUJ. °lc 2h com 00» of. 000 00m 00m 00m 000. Ho oooMHm .720. >ozuaommm CON. 00¢. com. com. OOON comm ooon 000.. 0000 d _ — r d _ _ — d _ « , ‘ — _ mamoowm . moonmncopoo... mnfibfiosl muopoanOI: 1 _4J___Aqdd—<fi — .d m. _ .O md to «.0 0.0 BONVOHOSGV 25 Ono 00h HH> ooomfla $-23 >ozunow¢u on» com Ono 000 com 000. CON. 00¢. 000. 00m. OOON oonN Goon OOO¢OOOO — 1 — _ — ‘ _d_—‘_— _ d _fi~qq—dq——:_—_ ~— ommmfiWm . mwlmw v.a.n «moflpoano ampoom now; owflooaao Hmoooooawmo Eoom poooooo ooflMflpcmwflnm my 0; o no lJ l to 1N6 .. 0.0 3ONVBHOSBV t.) .31 In one run tho rooctiw nixturo 11:13 added drop-visa to 3500 g. of ice water in a five-liter ‘oil‘roc-n 1...3«:1 flash eqdippod wi .31 one-lily... «iditbn fumwl, stirrer, and a dry ico flap. The lmos'uro was roluc. cod in the syn tm and some liquid m3 dis tmod into tho trap. The trap was found to contain only chloroform and labor and no um'aac 150:1 cy'c lo progy'l 6:11.01“ m3 0 3 . Stmcture Proof of h-Chloro-a methyl-3 -buton-2-ono To a stirred mansion or 3.8 g. (0.1 mole) of lithium alumllm hydride in 50 all. of anly‘c; c.2013 otnor was ad... ’«oi 10 z. (0. 012521319) of h-c}fl.oro-3«scthyl-34Juton-2-ono. Tho mtctura was stirred for four hours and than hydrolyzed in tho Haul]. Will-'31“. The :1 char 1-1213 doozmtod and driod over meow mllfoto. Aft-3r removal of tho solvazlt tllo' are me distilled 9.2 g. (93;) of L-cli’ooro-3-mothyrl-3-buton—2-ono, 11.11., 65°, 1:155 1.19370- &. Calc'd. for ($5390.21: C, 1.9.321; .., 7.532; Cl, 29.5. med: c, 1.9.73; 1:, 7.735 Cl, 29.6, 29.6. The infrared absorption spoctmm (fig. VIII) showed a strong pool: at 811; on. the prosonca of lilich indicatod a tr " ‘ otitutod olefin (3 2). Duo :11. of this c0211; and ms pl... cod in 50 ml. of 311,3 o+ Ion-cl con- comm 575 sumo ni‘to‘ate. 230 Weill-doze of silver chloride was obsarvod. Howavar, man 011a 1111. of allyl chloride was trutod in a like war a precipitate fol"n mod Meeting that the former commmd probably did mt contain an alJylio chloride Mtion. 0"} 1. u --.‘ .' ‘l t ‘ X4 , . ‘ . . V ‘1 ‘- ‘ l . . t . u ' ’ '. A ‘ ‘ . . o. «1‘ n I - 1 . . -, ..,.- ,1Hu‘, . , , . ’ ' y . '. :0", O 3 1 -h r ‘ 4— -. - . . -. . a . . . ~ 0 - ' q - ‘ ~ o. . ‘ -v 2 ' T ‘ v 0 1 1 I- .v it .1. -4 ‘ A. . ‘ I ~ in ' . . 1 A . -.. O . .. - . . . 1 ' - 1 . .- .‘.. . . . i; . . - ~ .7 . I - ‘ .1 .' . .J . 1. , , - a . - ~. — »- a- 1‘ ‘3 . . , 4 .. . (o , ‘- ~ 1 .‘ ~ .. .. t r - v r 3 . . .. - . n ... o d C 1 . . ... 27 000 02. , 3730. rozuzoum... On» 000 00m 00m 00m 000. . DON. 00¢. 00m. 000. OOON oonu Goon ooo¢oooo _ H i - q - _ u—_q4 ‘ _ _.1__—~—_qqq_: _qdm~_ .. mumoswm «Hon munmpbon. mIfiBme... mlopoanoln l 1 l d 8 to Nd 0.0 SONVBI'JOSGV '0 ca 218 l-mphtm'lnrethan (3 azfimtivc was prepared and after Next/8m- 0 11311151911 from petroleum ether maltac‘. at: 97-98 . 1171:}. 0mm. for c1032... 272:1: c, 55.31; II, 5.55; 2:, 14.824; ‘n‘ ,A an 9‘, «E‘OJJO - 3 If 1 f." ,v-’ . } FW' L, 00.3.3] 1:, 303d; }3, Joli; Cl’ 1202C. 1:. Maximum: «3330ng «n-ctygrl-3-bgt‘n1-ggong Five grams (0.01:2 mole) of h-clfl.oro-3-meflvl-3-b~.1tam~2-ona was placed in 25 ml. of umydroua ether and ragweed with hydrogen (50 p.a.1.) aver platimn oxide (0.2 3.) catalyst. Aftarr one-ha): hour 0.25 mole of tudrogan m abuorbed, after which there was no further uptake of hydrogcn. mo ”hm m filtered and there was distilled 2.1; g. (6’73) of 3-methyl- 2-butmol, 5.13.1 chm. 106-119", n35 1.39M (lit. values, 1343.,” 110-1212", ago 1:3973) (1:1). The product contained a trace of chlorine which could not be: removed by aimla distillatinn. 13:. WW and l-fiaphthylurethan mm prams-ed and aft-:11- mmuutmn from petmlcum ether melted at 65-67" and 107-108° rem-1.7 (m. values, 63° and 132°) (31). Mixed melting point Mmu with samples prepared from Eastmn "mite label," 3mm- l-h‘lnol M an depression. ..-| ma ,. .3 4.2- a 1-- ru-1.__, 3,1 ,4, L-.......-..:'i-—c vi. ; ...l_‘.Jl .,.-.l...:°.-.-3 A column containing 133 z. (1 male) 01! alumimm chloride, 120 g. (1.3 sales) or acetyl chloride and 80') ml. cf clflnmfom ms pmagarad in the usullmnnm' at 5’0. Allyl chlormo (7?; 3., 1.0 mole) was added drop- Iin. dtb m. Tna bright red solution thus formed m deceive-ed N"; . . Q ‘ . Q ‘ . 4 o - . . .. -‘ - . l . -‘ s " ‘ -v ‘ ‘- ' . ‘ ‘ ‘ . ~- . . . - . - ,v N | . . . ~ 1 , . . 1 z - . . .. u - g '1 M . . . t w . A . ‘ - .. A . a ' 1 n -. ‘1 I v - a u :w . ‘ . ‘ r ‘ . .c, (l ‘ .. v -1. n ,_ . . . ‘ . _ . ‘4 ‘ . A . ‘ ‘ ',, .l .‘.‘o ". ..’ l . . . -. 4 7‘ “ ‘ . ' ‘ - < i — _ h . t I . - u _‘ .- . ‘ v . , . . ' v 9 , . ‘ 4, . '- .. , A: ~' ‘ ‘ M ‘ ~ 1-: . * ,— . .- ' . ‘ ,_ a‘ '. , - . , ~ - — .- .4 .H... ‘)~ . . - u ' . , f g . ‘ . . ‘ , - ~ . . . . I - . I. .1 ‘ , . a ‘ ' 1 . . _ . , 7- ' I. . . , , - , v 9 4 '5 _. - . v 4 n A a. ‘4 I Jr. 0 «v - . . .4 . . .4 w 1.. ‘9 ‘l . 9‘ - V . ,3 u S. -l 3. h - ‘u I ... o and mob-ad in the usual mar. After being dried over calcium chloride m. chlorctoz‘ In: distilled _i;!_ 2333. Some decmmocition m detected mwmummctu: m. marmxryme ottauptad. The product us, therefore, coded to 3-3-0 m1. of 20:! sodium bicarbonate and featured, with vigorous mug for one hour. The solution was cooled cm, IWM' not! the aqueous m was extracted with other. Tao mic 1m were Mined 3nd dried over magnesium sulfate. Arbor mm of the other there we obtained 5 Mot which did not mutant decomposition, below 60° at 3 m. mount. no product, chic): m mite viscous, m not investigtod further. 0. Acct- . l -1‘i offlomcrckmromne 1. 1,1-Diohlorocyclopropcna Cl\ CH. ../ °ozwaoumu— Ooh 000 000 00m 00m 000. CON. 00¢. 00w. com. OOON OOON OOOn COO? 0000 H u — — fl W q u — - — —— HJ —-—udq4q_—qd—: onoonwm .oofihoaso thmow spas mammopmoaomoonoagowolaaa Eon“ powwopm onmeCoch: - ~4WJ . 8 l 0.0 $6 v.0 Nd BONVBHOSGV 32 placed 590 g. (10 moles) of 83:3 hydrazine hydrate solution and 530 ml. of mt‘mmol. One kilogram (7.5 moles) of chmneldchgnie we added drop- wine with whirring. The mixture was rammed for three hours 9.3161 Allowed to Itsnd overnight at room tetmeramre. The mixture was distilled an atmospheric pressure we the material boiling from loo-170° collected. the oil thus obtained was pushed with 200 g. of ice and 500 ml. or 1.1 potueimn parmngyunato, dried and distilled, b.p.3° 77° (lit. value, b.p.;¢ 17.50) (3). The msh and distillation were repeated until u constant "motive index, :32 “1231 1-5311: (B3)). A yield 04‘? 301; z. (3653) was thus obtained. 1.5308-1.5310 was 0‘3 tamed, (lit. values, 2. The .huotion of Phenylcyclopropane with Acetyl Chloride me ecetyletion mixture was prepared as previously deecribed for the reoctiou 1,1-dinethorlcyclopropene concept that the reagmte were added in one mole qmutitiee to 750 ml. of chloroform. Phexvlcyclopropane (118 3., 1.0 hole) m added drapwise to the mixture at 1‘0.th neverel milli- liters had been added the temperature rose mainly and hydrogen chloride evolution as detected. The udxtm-e was cooled down to -2-'5° 1 5° and the addition continued, and me accoxrxmnied by n slow hydrogen chloride evolution. The nixture was stirred for one hour after the addition was cowl-ted cud then poured into 750 g. ice and 200 ml. concentrated hydro- chlorie acid. The orgnic layer as separated, washed successively with 500 ll. of Inter, 500 m1. of 1553 sodium bicarbonate, and 500 m1. of outer, and dried over calcium chloride. The solvmt we removed a E... end 101; c. of product no distilled, mp.“ 120-130°.'1'he residue did not \I .4 ‘ . _ ._ o . r v e v ‘ . u . I» O u. . o. - .v' 1.. o z 9;. - . o. 4 . ... ~ V d r. . . .3. I . .. n. a u .4 .. .,. ..- u. . J 1 C . . A 0 .. r... .c .c n . u o u. .- o _ l I .- . w w! _ J fl - I . A. . w . . . I v I I 9‘ I. e . .. c . hole 5 T_ t . . l t q o I .p . .. a .0- . Q ~ .— . c f .b :- .\ g . o ,. q i .. u 5 . o u . .. . .. _.. . . .. n l u r n . . A . .. r . . .. .. a n i y . . o. I i. . n .- e 6 ~ . y .. I ‘ L N . f r A . . . I . I . .u r A A cc , . . x o. . \ - L d . . . . . . . 3'. ~d w.- n '5 fit 0 . . . n _ u. ‘1 7?.) .3. .x .. .. .. . o o o . c ‘v _ E s. k u ‘, . e I .0. . .6 r.- \ u .., _ . 9 o .. a H. . . . . I a c .s .. . Q I . I 9‘ §. A .5! . I. . v I: .r 4. r . .‘ to. o o I Lr . .n. J x . a x b: to distill below 153° at 2 m. and aft-er striding at 0° for several izys, gave off some hydrogrn chloride. Attempts to enema this tau-y meme were 11" itixout moo-cos, nor 11-1 rci‘lmzmg with 1373p 0+1! #3311112: carbonate change the nature of this 2111: 3r£2.11. Fractionation of the distillate yielded 73 3. (113,2?) of “- ,-..o‘r'o,..Jhce..omcuono b.p.3.5-,.9 1‘ -119° , mp. 35-3 0. This (10:19:14.... was r‘ClZ’VLuL-LL“, from ct‘muiol or petroleum other by cooling to 0° . cg. Gains. for engine: 0, 82.1.73 1:, 7.53. Found: C, 82 .271 11, 7.53. no infrared absorptionso spootrma (fig. 1.) ms 111711.112 ed to determine the mturo of the product. he cortmorl peek at 1630 cm..1 was the basis for believin; that acetylntion took place on the phenvl ring. 1110 2,h-diuitrop. .onyl. wirezone was prepared and after recrystalli- sation from ethyl acetate melted at 219-220° . The compound was dissolved only after prolonged rei’lmzing. m.0a1c'd. tor can“: 1,0,: 0, 59.98; H, 11.73: N, 16.16. Found: C, 59.88; H, 11.90; 11, 16.25. The ultraviolet absorption spectmn (fig. II) in 95% ethanol showed a 1 I: at 265 m., 6 16,000. 11113 use cornered with the ultraviolet abnorptim [pectrun of a freshly distilled sample of Eastman, ”white label," acetophonone, 7s m 21.2 1111., E 16,000 (lit. values., ‘1» max 21.01111. G 13.0%) (115’). more on also obtained 9.5 g. or mt'n'ial mp.” 125-131°, ago 15668-15532. This matm'inl gave a positive Beilstein test. 112:: infra- red absorption spectrum (rig. XII) was very similar to that or . . .4 . O I p _ . . t . . .. ~ Q ., ‘ r u— . I .. . . .1 o . I . O . n . ' t c . I A - p q . _ .. .J.I- l . . _. I .. a . . . (I. . .s . o 5 .1 I 1 v . . :A. A A . O . a n I i I . . . .. o . r p. .. v. . _. . s . . Q n. o .. o A I o . w \ . J l . 1.. ... 1 . t . . c l . 0 d o . s O . . . h. ..< .l m .I . ,o . O s ‘ o . '. ‘ V. v < n‘. v C o. .v- 0‘ t. . § ’ I _ . o . . u . 00.. o \\ . 1 . _ ‘ . O . Q — u ‘ p k... . u c . , n , . . . . -.. 1. O 7‘ .. ... . . ‘ . l _ g 4. - ¢ r 1 o . a .u. 3h x 0.33.1 .728 52331... Ono 005 09. com com com 03000. 00: 08. 03.8180. 80m 003 000» ooovooon _. — . 1 _ u d d—_qqdqdqfi—A___.___.‘_::_ .W. 0.. 0.0 no .o .0 flow «a w m .a 3 .5: mo. noofipoagowppop connoo. 5 Rm .mnoamnmopmomahmoomoaohoum H 11/ .I .J E 8&2 1 502334; ovn Onn own om Gen omN om~ ohm omw Onm ovN Gnu CNN a _ 1 . 1 _ 1 4 o _ o q n 10v ion Om % I. 12W N S m 5 10mm. 0 N H -5... L00. Homozpo mmm 5 peace 3.. x mm.m «econonmopmod. “HH 3.55 ml Homogpo mmm 5 “macs OH x .34 ammocozmopmoddfiopQOAuoholm " H 9550 m: 36 HHN moemflm .720. Bzuaowcm 000 com com 000000. 00: CON. con—003000. OOON 09mm 000» $00.00 q _ \— _ _ . _ q\._ o o _ _ _ __ _ _ o _ .1. a; _._____ q on; 4 .0 0.0 0 .0 nd 7L4 mwmoovm . HmHImmH m.m.m.p «mmwnoago HApmom sows mammopmmaohonCmsa 509% #050090 ooHMHpcmoficp BONVBIIOSGV k) '4 E—cycloyropylncetothonone. This 1‘ notion did not cryotallim when cooled 0 n - _ --. _- _ ._ _ . to ~78 , tut instead for-213d a g "‘8. 00-3' ‘21,; with p-cyulooropylnc- “etc- rhenone did not mince 11:52 cmezwuation. T1113 product was not izrveeti- gated further. 3. Stmcmre Proof of p-CycloPropylacetophemne c. 01111;: "t ion to 34.”; cloyrcgi’izer'zzsoio ..oiwl One m (0.036 mole) of p~cyclepropyhcetoyimnone we added to a solution containing 20 12.1. of: water, 20 ml. of diorama, 12 g. (0.3 mole) of sodium hflroxide and 9 g. (0.11 mole) of bromine. The mixtwe was stirred at room terpemture for five hours, after which the dime we attracted 'Irith ether. The water layer was acidified with moth‘ochloric mid, decolorized with sodimn 121231112?“ to and the mixtue was filtered with motion to yield 0.9 mm (83:3) of g-cyclomopylbenzoic acid. After mmtnllination from ethanol and inter mixture the prochict melted at 157.1530 (reported value, map. 1574530) (215'). - Nmtrnl. equiv. Calc'd. for 01011100,: r2.2. Found: 1614, 16? . m.031o‘d. for amend... c, 71.33; H, 6.21. Found: 0, 73.82} H, 6.36. hb. Oxidation with (111“ch inde Sit was (0.0375 mole) of p-cyclopropylacetofizenone no added to a solution of 33 a. (0.33 mole) of chronic oxide in 100 ml. of 502:5 acetic mid and the metro was refluxed for eight hairs. The mixture on. than . .i ‘ - .... .V A f |_ '\ ‘ .‘ a u' . . \ A; x f., ‘ 14.4 3 . . . . - . . .4 ... o q , A _ p . ‘ ..w o l. . r ' v . . _, g r , . . ~ . ‘1 , -. 4 ‘ On . . .— I ‘ v r . a. t . .t ' . ' ' D . .0 . ' ‘ . I A l I l ‘ >J ‘ ~ . - ‘ < - . I‘ ‘ ‘ o . ‘ .1 E ‘ 1 ‘1 ,.~ p‘ i ‘ ‘ ‘ ' 7| , ‘ . ‘ . . -l . ~ ‘ , , . - . ". g. 4‘ , _ ...." I I. . ‘ . . r \ - ‘ _ I I . ~ A . r c O _r ‘ V - A. w . , ‘ _‘ ' ’ ‘ ~ 'L . r f . . ,. ' .. .. ' ‘ ‘ v - ' A ' o_. u , f ' . _ ' . ' I ‘ n 1 . ‘ 1 . ‘ 4'1 . ‘ .. .. . ‘ . .- I . _ ‘_ h . l‘ ‘- . I 7‘ _ u ‘ .0 . I ’ . . ‘ ‘ l . . - L ‘ K r " ‘ - . _. . ‘ . . z 1 _ ‘ A, A .1 . . ~‘ \ {3' . ‘ ,. ._ v I 1‘ a ‘. . I ‘ ' 7A. ' . ' ‘ rt . -- V - -- _" ..- ” ‘ v.- . .. u’. . - ... ‘ - u ‘ . C. ' x . .. .‘ . ..~. . t- ‘ , :5: . . _ . .‘ - ‘ ‘ . . n ’ I I ‘ 'r , ‘ l . “ ' a t" .. _. .. .. r ) . 2 I . .. .. ‘ ' ; ' -A-. " J '- . - .. _ . '1" 'c... .- P. .‘ ' I " ' -- I a ' ' ’ \s . . _ ‘ _. - . _ ‘ l . I _ . - 4b”... - .. \~ _, .’ . . O. 1.. . . , - t ' - 1 '5 ; " - . If} .x 3 . . J ’ ' . .- ' l ’ o . P ‘ f I z ‘ . 0 — , 0_._ «‘0. ‘ ‘ F) ' . > r . .‘ .c- I . j ' v 5.. ' 1‘ .. ~ ’ '4 3 . ' A ' - I poured into 100 g. of ice and tilt.- rod 111 th auction. The precipitate was was ‘1ed with miter and mood with 20 ml. of ethanol on I flew: 113* h for one-half hour, filtered, and the precipitate cashed with ether. 'I'l-zere was obtairhed in this mmer, 3. 3 g. (61%) of terephthalic acid, subl. 280-3 o°o (111. value aubl. b01011 300 °) (L6). Neutral. equiv. Calc'd for CGH‘ (000mg: 33. . I Found: 85, 85. - fig. Calc'd. i‘or CBHQO‘: C, 57. 85; H, 3. 611. ”Found: C, 58.35; H, 3.70 The dimethyl ester we prepared according to the procedure of Smith (L?) and after recrystallization from methanol melted at. 1.2.110 (21115.!!! mp. 1.1110 ) («‘47). A mixed melting point with the ester prepared from on outhcntic eervrple of terephthalic acid gave no depression. III. Rotations of Cyclopropanc With Sacral Types of Chloridee l. hChloroncetyl Chloride 3 ‘ This compound we prepared by the procedure described by 13.0. Brown (117). To a one-lit er flask fitted with a 25-cm. heated colnm packed with glass helices was added 6311.5 8. (11.5 moles) of benzoyl chloride end 233.5 x. (3 moles) of chloroacetic acid. The desired acid chloru-e 1m distilled from the mixture and collected from 95 to 103°.01mem 'redietillod, 217 g. (64%) or product, b.p.1 am 103- -,n105° 01.11550 (lit. values, b.p.76° 105° , nDO 1.115141) (3.18) was obtained. 39 2. The reaction of chloroocetyl chloride and oyclopropane The procedure m osoedtially the some as that described in detail for the reaction; of .cetyi chloride with owlopropahe. From 22.6 3. (2 moles) of chloroocetyl chloride, 266 g. (2 moles) of ehmdmm chloride end 90 c. (2.2 males) of cyclopropnne in 800 ml. of chlorofora there no obtained 2147.5 3. (69%) of a mixture of chloroketonee, b.p.3 70-90". The resultant mixture of chloroketonee could not be fractionated et 3 m. of mercury withoht decomposition. To selectively dehydrohnlcmte m F-hnloketonos, the chloroketone mixture we added to 500 ml. of 20% eodiun bicarbonate Iolntion and refluxed with vigorous etirring for one hour. The mixture 1n cooled, the lower layer removed and the aqueous layer extracted 111th other. The organic layers were codained and dried over 3351681111! sulfate. After removal of the other there one obtained, by distillation throuw a 25-cm. column packed with 1/8” 31888 helices, 55 g. (16.5%) of l-chloro-B-methyl-B-bnton-Z-one, b.p., 56-57°, 11:1“;s l.h692-l.h700. £0 Calc'd for 65237001: Cl 29.9. Found: 01, 29.9, 29.6. The infrared absorption epectnm (fig. XIII) chewed peaks at 1700 can...1 and 1630 on.“ finch ere characteristic of cfiqmeatureted kotonec (32). The compound also gave a positive iodofom test. The 2,11-dinitrophmyl- Wane we prepared according to the procedure of Johnson (30) and utter recrystallization mm methanol, melted at 121-122°. m. Celo'd for 6118110 mm: C, 1111.233 H, 3.72: N, 18.763 01, 11.87. round: 0, 1111.03; H, 3.91.; N, 18.53; 01, 11.811. I - o . 1 L a e u o . _ v .- _ , . .. 2. . ‘ . . - 7 l 1 ‘ . I O . 7’ I A ' . . e ' uh - - ' 7‘ I ' " . ’I‘ ‘ l . , . l n‘ e T. . I" *0. . ‘ - ' \' ' ’ ‘ -o . ,. . a» 0 D “ ' I -. - ‘ _4 ‘ . - r . . y‘a "‘ ‘ ' ' ' ' _ - _ ,. . ‘ '- .1 “‘0‘ . ' . - . . n ' ‘ l “ . - . .‘ p I l l - 5 .‘r 0‘ c ‘ . “ ‘ r .' . ‘ _ n . ' . ' . O - g .- .' . ’ e A ‘ ,. .. . . I . ' , . , .' » r '0 ‘ vs-‘ ~4 ~‘ “ I I ‘ .’ L. L h - . . I ' " . ' l ' ' ' ' '. _ ‘ ‘ . _ .f. v . x Q'. -~- - V ’I ‘ 4 5.. x‘ «I :13 9 ' ' I r ‘fn ‘ " ‘ c " ‘ 4'5 V . ‘ A .. \ ',,. _ L1. } o - I . " . “ , . . - . A- . ’ ~ 7 ' >— J ‘ i r . . . g ' l' . . ‘ - r . ' .n J. a . , - - ... A ...t ,-. . ' " I r v p, "v iv . . . ._ l ‘ w ‘ ‘ v -"1 . . o f ‘ e . Wu ‘. l O ' - ‘. w hO 000 005 00s 000 000 com 000 000. 00: 00m. 00m. 003009 000m 00mm 000m 000v 0&3 HHHN moswfie A723 Szuaoumu fi — 4 _ _ _q—___—_d___qd_~_fi—q____q:d _ in 11111 1 1111!] l _L l oemmsvm «occlmloopsnwmnahspoalmlopoanola n. _ 0 . . 0.0 0.0 0.0 to n.0 N0 _.0 0.0 BONVGHOSBV There we also obtained 52 g. (ll-15) of l,5-diohloro-2~pmtenone, b.p.3 - 76-79°, n55 Lina-1.1.770. ' ‘ 53;. VCalo'd for cfiyfioclas at, 25.8. Found! Cl, M43. lab-7, h2.h. The 2 ,h-dinitrophexvlhydrazone we prepared and after recrystallization from mature). melted at 105-105 .s°. A mixed melting point determination with the lame derivative obtained from an independent synthesis gave no depreeeion. 5.3g. Celc'd. for Cnii’mo‘ii‘c'la: C, 39.1.3: H, 3.613 N, 16.72) Cl, 21.16. Found: 0, 39.1.7: H, 3.66; N, 16.87; (:1, 21.10. Attempts to prepare solid semicer‘oazonoe of the two chloroketonee, using the method described by Shriner and Moon (31) were wacceesi‘dl. The infrared absorption Spectrum of this product (fig. XIV) was identical to flat (fig. IV) obtained for the compound then synthesized from hoolflorobutyryl chloride and diazomethane, except for a small peak at 1635 on." in the letter which we probably due to the presence of Yi-butfirolecetone which absorbs strongly at that mve mmber. 1 3. Proof of structure for 1-chloro-3-1nathyl-3-buten-2-one a. dro eeretien . ’ Six me (0.05 mole) of l-chloro-B-methyl-B-buten—Z-one m reduced by hydrogenfat fifty 13.3.1. and room temperature, using Raney nickel as the catalyst. In forty mimetee, 0.08-O.l mole of morogen nae abeorbed [e e r” I' r r «3‘ A I ..- - . . — o . 4,. . ‘. 0 ~ - ... U . . s a I e »‘ , I». .- l . ‘- e 1'. u e v' . A f A. o - Q ... .. .15 :1 _ . .. C Vfl- “ . .7 4‘ 1 I" . - u . v a | A . .. .‘ . . e 4 ‘ a .. -.. 142 $-30. 522402.... 000 00h 00k 000 000 000 000000. 00: 8N. 08.00289 000w 000N000» 0090000 - _ q q 4 u . qququqdqu—uq-uu_—-44~——-qq mumoovm .oaenpofi — Allll .8 0.. ._ .0 0.0 v.0 n.0 Ioueflo new: evapoazo Hhhhpopou0H50I4 80mm mcocepnmmrmlopoanowmlmqa .od :2:me 8e 02. on» So one 030880. 00: 08.03.8182 88 3380» 89.83 _ u _ — _ _ ‘4‘ .fid-_-_—-qqfi__-_d___::-— 8. n j o o d d o o l..° L commode .ao «mowooano Hmpoomonoano sew: onwaouaoaoho 80pm odocepcomlmIOHOHQOHnnm.H Extender”. . SOMUOSBV h} and there we no further uptake of hydrogm. The solution was filtered and distilled to yield 2.2 g. (51$) 01’ 3-mottlyl-2-butanone, b.p.1 atm. 9h-97°, 111235 LhZOh. The 2 ,h-dinitropheml‘lydmzone melted at 117-1180 (lit. value 117°) (31) after recrystallization from 95% ethanol, and did not depress the melting point of an authentic sample prowl-ed from freshly distilled Badman "wh to label" (methyl impropyl ketoneD-metmrl- 2-butanone. b. Reduction with Zinc Elevan grams (0.09 sole) of the chloroketone we added slowly to a vigorously stirred mixture of 20 g. of zinc and 50 ml. of 50% acetic acid. The mixture Ins stirred for one hour and then filtered with suction. The filtrate we mctmcted with three 25-1211. portions of ether. The com- bined ether extract ems neutralized by the addition of solid sodium bicarbonate to a stirred Madeira of the other solution and enter. The other layer as decanted and dried over potassium carbonate. After re- ml of the solvent, 5 g. (65%) or 3-mothyl-3-buten-2-ol as obtained, b.p.1 ate. 111-11110, rigs 1.1.225 (lit. values, balm,“ 112-1130, n12} 1.11290) (19). The infrared absorption spectrum (fig. XVI) of this product is identical to that or 3—methyl-3 -butene-2-ol obtained by the reduction of 3-methyl-3 -butene-2-one with lithium alumimlm hydride. The phenylurethan and the lemphthylurethan of the 3-methy1-3-buten- 2-ol obtained from this reaction were prepared according to the procedures described by Shriner and Fuson (31). After recrystallization Ron petroleu- other the derivatives melted at 66-65.;o and 97—98° respectively. «f, I . 1 .e ‘ . ....» . i . r . 'A r - . .r ‘4‘ ,o .0. u u .V . p ... I v v .v ;. 9 . e 1 V INH' 3. .‘.‘:v- I u u‘ an Ex 2&3 :52": Bzunoumm on» 000 nx3_ 00m ommnxxz 00: nxxu oom.oo«.oon_ q u — . . _...-44.:q_qe.q:_::: _ r... “0.. .o 1 no “.3 to no lllll No ..O 0.0 memos?“ “Houmlcmpsnlmndnfimzlm OOON Down 0000 000v omooo BONVGUOSGV The same derivatives prepared from the alcohol obtained from the reduction of B-ne‘thyl-B-butm-Z-ons with zinc did not depress these melting points. Bqnethyl-3-butsn-2-ol phenylm'ethan M. Cale'd tor cannon" c, 70.23; H, 7.361 N, 6.83. round: 0, 70.00; H, 7.30; x, 7.52. 3-methyl-3 -buten-2-ol (lmphtbqlhrethan Anal. Calc'd for Gunfioaulz c, 75.28; H, 6. 713 N, 5. h9. Found: c, 75. no; a, 6. 673 a, 5. 63. ' I ,6.“ 2m ' than 0! 1mm-2-bnteno2-ons from m Iheprecemreneedus thatdescribedbyhndanandtraiv (26). a siren-e of 700 g. (10 holes) ethntanone, 60 g. (2' soles) of psi-aton- aldehydeandSnléotiflpotauiushydmideus’etinedatatmperature between 35° and 1.5‘ for two hours. The solstice .... neutraliaed an: acetis acid and the mess butanene removed by” distillation. rive milli- liters of 851 phosphoric acid, 0.5 g. of copper powder and 0.5 g. or hydroquimne were added and the residue distilled at a pot temperature of 120-1300 , under nitrogen. The distillate ms inched with 51 potassinn carbonate and dried over potassium carbonate. There was obtained 60 g. o of JmWI-B-buten-Z-one, b.p.1hm 96-100 , n35 1.15192 (lit. values, 13.1).ng 98°, 21%; 1.h163) (50). d. 3.qu gr g-Me‘gzl-i-butm-z-one with 21:! a From fifteen was (0.18 mole) of 3mthyl-2-bntm—2-ene, reduced bythesasepreeedureaapreviouelydeacribedforme radiations! a r , - a . e b : . e ‘ f. ‘ - 7 e . n F l , i . . . l - v I . 1 \ 1- ‘f . ’ V ’ v ‘ 4 .. A I . e A ‘ v a O l - ‘ .,6 _- s a... _.. . . . - .4- r - . . - . ,7 - ‘1 . . .—. ‘ ’, . I ’g ‘ A I , . a ‘ f p * . ' ~ . . - ~ - Hy ‘ ‘ ‘ ‘. u , . , h - y e . .. . ‘ .4' '. . . - , ' . r - vev 7 ‘ v. a} P. . . I . . a o .- -.. '8...» - t . n . - s 0 O . e - . I 3 . ‘ _ . ‘ J ‘ .~ >6 “ . , i ‘) A I n .. . Q I 1‘ .‘ , , h . , N 4 , - - 'II I 0.1 7 .e > g . . > W - > y,- 3 . ‘ x ' . ' s . .-.t. 7 - , “ | . . . t- - r . - A in 4 ._ . e... - V-‘ 4 L ‘ . . ‘ f r I“ ..< .- n. 4 ~ ~ - - u - 'x ‘ r“ . - . . . e on ‘ i -.- a . ‘ l A v: ‘ ' , 5 O ‘ L- ‘_ A (a ‘ , ‘ M u ' ' ‘ 'ie. . ‘3 . a 1 'e I . I A. 0. e- . a ’ ' 1 v e at ~ . - . r ’ 1:... ' a! . ' . ‘J 1'" . '7’- -_ I I“ 1 ‘ ' n —. ..- ..fi A ' — - o ' \ g: I. L I .‘ J ' ~ - . I ' a uy‘ ;- i re \ ' ' . O i l O I ' . a‘ “ W s... I. ‘ . l I O , b s A r” «.. t .... .‘ .4 \ N. .1 . " u . " . \ . e ‘ . .s ,0 , . 'r-‘ 1.. 5 e ,. ' ‘ ' I ‘r ...! L, .‘- . . ‘ I ‘a‘a’ I . 0 ~ " - '1 . - “r , ‘ , l L e ' - x . g . .i Q a . v . »-¢ ‘1‘ 4 .- ' . ’ r. a . t ‘ N u 4 . i. _ J‘ . ‘ ‘2..- :. . . Q "Q -_ u 1’ “n: at - - «...! _ 4 v. ~ . ‘ - .1 f ‘WI . . flap, I v. c. u. l- s. . t . y u 4 ‘ - f _ . . ‘ '._ ‘ 4 ; . _ 1 . . ' a - J.’ g . ‘o v ‘ a 'J ’- . .. 'O . v. I _ g .. fl . x. . . . . ‘ . . alu . f.-.‘ ‘ ., . . . . . . _ . . . , A a .. , . ......w K ......J -. ‘-.. ~ 'c‘w . .- ’ . - ‘ .- K {n .. q , - . , - r . . :3 ul- , . r * _ ‘ A ‘ . o . _. ~_ ._ . _. ‘n‘ 5‘ i _ .e . 1' a v . . “7 ‘. _. .7 u ‘. .. A’s ,« _ c -_ r ,_ e. ‘u . ’ s‘. 1 i f“) k s' a'. . '1. I.” ~ 6" ' V J. ' - ‘1' ~“' . ' - .i.-- '- J , -‘“" I‘. . - ." e I e- ' ‘ ‘ a .I 7 . J . ‘. - , . . J t 9 ‘~ ‘ r ‘ - .. ,. . ,. ..- 7 .a . 4 - _-a ..- - .o- ....-. , . . .. ? r ' ¢| -' . ‘I ’3 .‘t- " G‘ I' .- e . . e ' ,3 _ . . 0-. . ‘l a- V J :3 ..', I... ' ‘1 '1 . - , f . ‘I s .4 '. . .~ . n v' ‘ a ' 5 ' " . I . r , 5 VJ ‘ . ‘ ”I . . »- .1 . a . i - .. - . , r ‘h ' ‘. .'."‘- ~11 a_- ..‘v . . - . ‘ ~f - . ‘.‘ .. v . . ( ,-Q.. , '. ' v . . _ ' , _'.. 5'!” H. , . f - — .— ' v ‘ r . . a (k l. ’: ’ a .. ‘ .5. ‘ ... ’ . ‘ r .. 3 -. -, ~-- 7. ' . ~- o . \qm .‘ I _ . \ v' o. 5 ,. . Q. .\‘ '. ' ‘ ‘ z ‘ 6 . 1 v’ , gob , ‘ "IP 4 v r .. . . é . mu. . , a - . ' A a '— I ~w ca. ... .‘ 1'. i ‘ V . {'3 v‘ . ‘ I‘" O'. - ‘.‘l'..' ,'a"0 \ ‘ " “ 35' i't‘DO & h . .- I " .' ,. ,. , ‘ ' 3,. ..-, r...“ . - q 3 l.- ‘ . . --- _ ‘ o ' '4“ o I ~ - c ~V‘ n .. y. - Q a v .‘ v~ - - y ‘ . ,. 2' g. i. .. o.l0' ’_ . 1 e . i ,, , r , ~ - . .. u ‘ .. .. , . -.r _'_J - ’ ‘ - laehloro-B-ne dwi-3-butan-2-one, here meal... ":illed 7 g. 57%) of 3-mot‘1yl-3-buten-2-ol, b.p., gm. iii-113,211; 1.1.232. ...—I.— 1‘-.. . ' n 7 , ‘L - _ , a- e. .’.tt...._~‘:r:2d 32:11.;313 of l .‘_-€.:‘.:Z.l:>ro-'4-1t:e..ol-2-butunene 1) £19 preparation of 5-2:”- ““333" “stead ciloride. This coupomod v.3 prepared using the procedure doecribed byK'b each and Brown (51). In a 2,. 0-511. round-bottomed flaekw mppod with black paper and equipped viii-1 a reflux cordmeer, was placed 53 g. (0.51 mole) of 113thwa chloride, 5'4 3. (0.1. mole) of mli‘m‘yl chloride and 0.5 g. of benzoyl peroxide. The mixture was tamed to gentle reflux until the *hydrogm chloride evolution subsidei. The products were separated by fractional distillation to yield 11.5 g. (1.31:) of the c-chloroisobutyryl 2ozzhlm'ide, mp.“ 394400.31? 1.113110, (lit. values b.p.‘o 39-400 (52).!1 “01.1135” (51), and 16 g. (2 2%) of E-chlcroieobutyryl chloride b.p..° 69-70°, 612,5 1.1.533, (m. values, mp... 69-71? 5:), 111301 .1.,-51.2) (51). This reactixm we ropth several tieee in order to obtain a sufficient mom of material for the following reaction. 2) The motif). c“ ”-cbal «rod-.311}: stay]. c?“ or‘. ' :e .. th €13.25}th cane. An anhydrous other solution of diazometiume we prepared from 82 g. or Il-ezi trosonethylurea, following the procedure described by Arndt (53) . The ethereal solution of diazonethane ms distilled into a two-lit”, time-necked flask equipped with a stirrer and reflmc condenser. When . the other residue became colorless the distillation was discontinued and an addition tunnel was put in place of the distillation apparatus. E-Chloroieobutyryl chloride (117.0 g. 0.33 mole) in 50 ml. of other was ,— >‘ . . o . . .- v. " . n , ‘ v H V . ' ‘ ‘ o. .4 . _. .9 . ‘ I 1 Q . u‘ - _ u u -. ¥ ‘ . 1 h . , . ~ . . ,7 ‘. - . _— u. .- - 3- ,, t V . _, . ‘ . . . . . .. \ . . . a z . . an r- . t , »_ J. _ , . _ . _‘ -Ju ‘ ,u ' 4 l ‘ ‘ O u ‘ V , _ ' n f ‘ v‘ - . v . , v' . . - - , ' 1 l v . . . . . ) L. . c ’ ' 4‘ ' a n- . . s , .9 . L .w . 4 O I ‘- u - ' .. ‘ , ~ . ' I . ‘ o , . . b ‘ . . I ‘ . I I ‘ Q 7 . - . . 1. - . ' . - . { . . . l y - . . ' . ' v- I .- . ~ . . - - . . h 4 . _ ‘ ‘ 1’ . - l . 1 . .‘ c . " o 5.. ' ~— ,. ‘5 . . c I. ‘ I ' i " I . , n ‘ . v , , ‘ . . ' .- . . 1‘ 0 . -o 7 . I 8 ~ - V V n - r. . 5t. . ‘ ‘ o' ' . . . . . . . . .4 -r‘ - ' I . ‘ ' a . . - . . . . , ' ‘ ' " x . . ‘l J ‘ .. . .o p -< A: . A " - 0L. ‘ ' ~ ‘ 9 . . -- ' - " ' ’ u . . . . '. .. -. .. . . ¢ . _ ‘3. . . 5 , , ~ - . o - - ... ‘ r . .. . . - 0 . .. .- u. 1‘ . ‘4, I ' .. - < ' . § . . - - y. - - . - , A o .' v d .- V . . . ._ . ‘ , .1 1~ * ; . . _ . . I. . . _ , y y , g . - ‘ r ' , 4 .'.. .‘ d, ' fr ' . , ' , ,. . , ..L .’ . r - s . u. I {I ‘ ' ‘ ‘ “ a t A . ' ‘ 1. .1 . ‘ 1 . 5 ' - \ ‘. ‘ . ; n i" A ... v ‘ t. . . C ‘ v ‘ - fl I. ‘ '7 1' I . . .2 . - v . . . I , -. - 1. § - . ’1 ‘ ' o 4 l ' ‘- : ‘ a a- . '0 1 '1 . ‘ . . ,. . , , ‘ . . _ . . . ; . ‘ _ . . , . t ‘ , .1 u . a : v, _ - ’. o ' .— . to ‘— - - . p . “ . . ~A .. . . . . *7» L7 , , - . . . . 0- ‘ .._, ... - . r - 1.. 4 . . in I ‘ ‘ ’ ‘ - - .r ,- ‘ 1 -4 ' p ‘ ‘ - ' w I . ; ‘ ' added dropuiee to the aeration at 0°. Tue reaction mixture was stirred for un additional hour during which tine a flocculmt precipitate formed. The solution and then setm'a‘ted with uiuydrous turdrogon chloride and stirred for an odditicml half hour. letter we added slow: to the other solution and the precipitate, 11011 was mtcr soluble, was separated by decanting the other from the inter layer. The after layer was washed with 10;; sodium bicerborete solution and dried over mgneeiim mlfate. After removal of the solvent four fractions were distilled. The two lower boiling fractions were cozdsined to give 8 g. of "A", 13.13., SEC-75°, n33 Lam-1.1.1.80 and the two higher boiling portions conbide at to give 8 g. of "B", b.p.3 75-530, n5) l.h~5h0-1.h65’0. .1 gal... Calc'd. for 05.17.863.333 Cl, L55. Found: A: 38.2, 38.1. 3: 1.1.0, 1.1.0 The infrared absorption epectra. showed absorption at 1790 cm.”1 for "A" (fig. NH) and 171.0 cm.“1 for "A" and "23", (fig. XVIII) indicating the possible presence of both a lactone and a ketone in "A' end a ketone in "B“. The previously mentioned tat-or soluble product was insoluble in organic solvents. neutralization of the tutor solution with sodium bicarbonate caused the mterial to become soluble in petroleum ether indicating that it me a week base and tl'lerefore possibly the product of _ a side reaction of the diezoketone involving the G-chloro ”- This pmduct m not meetigetod refiner. h8 HH>x apnoea $.20. >ozu30ux... 02. 000 000 com Ommooo. co: DON. 009 001000. OOON comm coon oooc coo» _ a _ -.. _ ___-q1—q__qJ—__—__q4__q1: mumeovm . mwlmm m.m.n .oqmgomEONmao noes oeflooago Hapmmsoomeoooaeosm Soto .e.gooooepm BONVBlIOSBV h9 HEN made .Tao. 529409.... 00¢ 00h SN 000 Can 80 00m 000. 00: DON. Don-0.0.1000. OOON OODN DOOM 08¢ 008 . _ _ _ q o d - _ qqo._J__:_.:._.o.]::: . n... 1 15111 0' 3 memosem . wimp m.n.n .oomnposonmflo npfie_ooflooano a opouaoooH:OIu Boom nm coapoohm A mixture of ten gram-.3 of ".3." and "33" was added to 1-0 ml. of 15:35 Iodide bicarbonate and refluxed for one hmlr with eff is iont stirring; in an attmpt to dcfi‘grfiomlogomte any P-chloro ketone present. The so‘ - tion we allowed to cool and mo detracted with three 25-1211. portions of other. The other extracts ware COlfijijlfil-fi and dried over mgnooium athlete. more was obtained 3 g. of 9. pr duct 12.1.3.3 140°. Ellie mtoriel hed a. characteristic ester odor, and gave a positive Boiletoin toot. The infra- red spectrum (fig. XIX) showed two oez‘oonyl peaks at 17340 cm.“ and 1710 cm.-1 and only a emu p‘flk at 16.30 cm“; for carbon to carbon double bond. This epoctrm me mini-co that obtained for l-chloro-B- methylbutme-Z-one from oi'zloroooomrl chloride and cycloprOpz-me. In View of the lack of clear-cut results fills method for proof of etmctnre W13 not investigated further. 14. The Synthesis of 1,5-eoioflloro-2-pmtanone I . The preparation, of [pollloro‘gatgnrl cfillogide from butyro- ighty-eix gmne (10 mole) of xwutyrolactone we placed in a 500 ml. flask fitted with a rofhx condenser and solid addition nook. There was added 220 g. (1 mole) of phoephormxe pm‘oechloride portionwiee from the addition flask at such a. mte that the exotherznio reaction did not become too vigorous. The reaction mortars me then heated to 120° and a distillate collected, b.p., mm 75-10;". than this distillation aubeided the pressure in the egetom was rechlced to 15 m. and 63 3. O (50:!) of h-chlorobutyryl chloride, b.p.m 67-é9°, n5 1.1.630 (lit. values, 13.12.15 68°, ago 1.15631) (19) me distilled. xHx wooden A720. >ozmnommu on» 000 000 000 0mm 000. 00: 00m. 00m. 002009 000m OOmN 000m 000v 000m 3 — _ _4 q _ _ ___~__14d_‘_~_~_~____dq: _ 1 l Lilli L411! 1 1 m._ 0.. 0.0 0.0 m0 ¢.0 n0 N0 ..0 eemmsem .=m= one =e= .oo escapee“ mo perpwmpp mpgophwown Eofioom Eco.“ “redwood oofiflpoeowcb BONVBBOSBV b. M\ “so-)fncm .nL-‘Aeo- C? 1 1:“: —3,: ‘1‘ lama," _:m~:‘tq «1.4..qu Ref—3.1 1;ml..‘1wf). .r u- -;—-;'-“‘. .9 ~ A... \\_.,\ ..-,J .. . -.-. .. 1111:1131 c210... :9 ed CL... 571:) ....l..13 An anhydrous ethereal solution containing approodmtoly 16.8 g. (0.1; mole) (booed on lit. field of 63;?) we prepared from 61 g. of Ndnitro eomté-‘xylurm as does: :17 1‘: ed by; amt? t ( r".0. Twmty-one mus (0 .15 mole) of h-chlorobutyryl chloride in 10 ml. of other was added dropuiee to the nhtion at such a mate as to contain a slow reflux. The odomlre we! (unwed to stand for two hours and then cooled to 0°. Aldus/drone hydrogen chloride we passed in for 25’ mimtos, during which time the yellow solution became colorless. The solution we allowed to stand for one hour, men lwdl‘olyoed by the slow addition of WW. T113 6 oiler law no doomed and 1-133th with 130 ml. 01? 1"" sodium bicarbonate followed with 50 ml. of water. There was obtained 15 3. (659,23) of 1,3-diohloro-2- pontamne,b .13., SID-63°, n33 1 Lmoe-lmu. The mom-ea absorption spectrum (fig. XV) of this modest was compared with 1,5-diol'loro-2- pontmone obtained from cllloroooot'l chloride and q'clopropane. 1:33;. Calc'd. for C 0228(31308 Cl, 143.8. Found: c1, 1.5.6, 1.6.2. line 2 ,h-dmitrcphomrl‘vdmzono 1.27.3 prop; .red 1' r emporioon also and after recrystallization fro 11 mo tiwlol 22131 old at 133-13350. 3. Wet]. Chloride The procedm'e need for this reaction was analogous: to that described by Sclmerling (51;) for the reaction of an alkyl halide with olefine. I ‘. 1 , . -1 ., . KCuV (‘3‘ s 'b $ny b .k ~ l‘n.< .‘I ... . , . - .' . | .. o . I i f , . . ‘ . .. . J I . .,. _ I . .‘v. . I a J 1. fl _ ‘V . ., 1 . ‘ . ’h. 4. V a A. J ! 9 J "Uri. . ‘u‘ ' ’ ~ '0 — .0 . . . .. . ' ' 1. .oo ' a .1. . _ ,,~ ’ c ’ n . I- O » - . O - . . V ' ‘ v I‘ ‘ ' '--~.- . ‘ . . - . . ‘°‘ I ‘ 1 .l ‘1 ' o m 0 ‘Av ~ ~ - . . . . 1 :7 . ' Q . .... (‘9 «id In a ans-liter three-necked flask equ ipped v1.31 3 dry ice cmficnsor, sti. ”raw, and ’dtmmtar ms {111696. 21.2 g. (2 moles ) of t-butz'l chloride and 100 ml. of chloroftv-m. T19 mixtum ms cooled to {50° in a dry ice- isaprapyl alcohol bath. The marinate: m then replaced with a at: delivery tube and 90 g. (2.2 mien) cyclopromne was paaaai in. The delivery in -e was replaced with a mam-2021191.” and aim-en grams (0.353 molea) of ”Wimm chlor de was added. Aft-err ten mimtaa the ebudmun chloride was cmp1etezy dissolved and the reaction mun-o hm yellow, imam taming m. The nfixwra was stirred for 15m hours during which time the mmum 1n the flask um um $1139 to 0°. Mar-tin :11. of. 50;! mthaml m then added to fins mixture tohydmlvyze. the .11an chloride. The chloroform hyer as oepamtsd from tho aqueous layer, washed with 100 m1. at water and dried war potassium carbonate. After the meted t-bntyl chioride md. chloroform me mad the I Met ma distiliéd 150511911! 19' metiom as shown in-Tablo I. M. Caio'd tor: 0,313.31: 0, 62.1m H, 11.21.: c1, 26.1. ' Foundl Fraction 0 H Avg. 01 Total ' _ 5 61.32 11.13 27.25 99.70 8 62.90 11.29 25.6 100.1. 11. 63.36 11. 28 25. 85 100.21. ’ T19 plots of termtura (fig. I3) and refractive index (fig. III) versus grams a: product distilled 35m? flat portions between 17-35 g. and 25-25 g. rem.ective1y.1'1o 1130‘." .9119 cm to both of these areas an mm’oara 12-ng however, graham of om of these, 111, In: not satis- Iactory for 0,3361. The 19.83 g. or mixed product obtained from this {1131 WI... . C .7 111. OF “.8323? ”1'77“" KID-0““ 113’?" 1n“; new-m 5" EV." ru- (ELI‘Jn-Ja. "51713333 A 75-0111. ' 13.10330 1""...1 1/3" 0:21:11 I U1 1 02 . 11318311 . 293113. mm» 14331121. JWPD ”-7 mm 3:2 LJAUL'V at) -r_- n-mn J‘&.'&—.od.a.;t W 11162166 2° 2(111. 153.) Grams ago $1 » 1 380-83 93 1.1 1.1176 2 15.13 90 1.70 1.11161 3» 1.8-3.9 90 1.00 1.3.179 1. 719450 93 1.13 1.1173 27.9, 23.7 S '» 53-55 92 1.73 1.11181 27.2, 27.3 6 2 755-65 92 2.35 1.11191 '- 7~ 63-65 92 1.1 1.3262 8 67-70 92 3.21. 1.1230 25.8, 25.9 9 : 70-71 ' 92 3.0 1.21253 10 ' ' 72-72 92 1.9 1.1273 11 ; 73-73 92 2.0 1.1238 26.0, 26.2 12 2 73-721 92 11.3 1.1291: 13 .. 731-711 92 11.63 1.1300 .111 5 711-78 2 92 1.15 1.1.301 25.2, 25.6, 25.6 15 76-82‘ 92 11.0 1.8301 16 " ; 86-92 92 3.6 1.1303 17 93-95 92 3.0 1.2301 18 97-103 92 2.115 1.11311 ‘ 100-110 92 2.3 1.3.01.0 ix.‘ ‘ “>-. .v morn)“ .65 “' Distillation curve: temperature vs. g. product from t-butyl chloride with cyclopropane HO" IOO '- OCT- .03- 70*- OO- 60 Figure XX IO I. 4380 L4360 L434O |.4320 L430 IAZBO IAZGOT- |.424O l.4220 IAZOO IAIUO IAIGO Distillation curve: refractive index vs. g. product from t-butyl chloride with cyclopropane 56 5? reaction is consiiorably loco tit-1n the theoretical yield of 302 3. Several attempts to idmtify too carbon skeleton by redzmtion of the chloride to an al.2211121, via the formation or a Grim-2rd roagzmt and ram-01y- cio of this product or by redaction wit-E1 zinc and acetic acid, did not yield a distillablo bw‘d‘ocarbon free of halogm. An infrared absorption epoch-um (fig. 23:11) or redistillod 101m boiling fmtiona 1-6 :5th clnractm'iotio wane absorption panics. m A 1' ‘ - Q .3? P 4.- " . 9-0-1 h . 11.—2:: 1. 0.11.4.9.- 98 113...! 0.935193131181319. A solution containing 211.3 g. (0.5 mole) or 12131113110le chloride, 67 g. (0.5 mole) of alumhrrn chloride and 500 ml. of chloroform was mo- pared in the usual mar. Stormy-dim grams (0.5 mole) of cyclopropono m passori into the solution at 0°. The solution 1:13 mintainod at 0° for 0:19 hour and than otirrod at room tamomtare for twolvo hours. The ndxturo was poumd into 1100 g. of too curl 130 ml. of concmtratod hydro- chloric acid. T110 (3:11.01 form solution was traatod in the usual mom to yield only nook-21:13:91 mlfom-l chloride» and loss than 1 g. of a mtorial 121161 boiled 196»... 120-153" 6.1 3 13231. 11113 mtam decent-12.6.1 bromixm in carbon totracl'dormo and give a nogativa toot for sulfur uhan a sodium fusion analysis was mdo. Ethaneoulfom'l clflorido , bufimcoulforwl chloride and pdtolnenoaulfmyl chloride) score 9.11 trad-3,32 1n 3 12111.11- 1...... but 2111121 to yield any significant mommt of promct. 58 HQ €ng to 20. >ozu30mmu Oak 000 000 000 000000. 00: 00m. 00900! 009 009w 00mm ooon 000w Doom . q a q _ _J -_——+__‘—d~_Jd—d..q_«:_ _ q 8 m... 0.. 0.0 0.0 0.0 to n0 1 IA LJJJJII! Ll N0 1 _.0 mummowu .mmonmm mm.m.n ccmaopmoaoho new: mownoano th 91» Scam ouapoazo Hhxau oofimapnmufiab 1 0.0 BONVBUOSGV 59 D. rem-1 P arohlorato l . Aoetyl Pml'alorato with Cyclopropane The procedure used in this (if-5932311531113 to prepare the acetyl par- chlorate m that described by Birton and Prom (55). Ton and a half pram (0.05 mole) of silver pox-chlorate, which was dried overnigit m phoephoms pwtonido in a vacuum doosicaiwr, was placed in 125' ml. of freshly distilled nitromciimo. 011:. grams (0.076 mole) of acetyl chloride as added enzyme to 2316 9611111211 at 0°. n16 mixture was allowed to stand for one hour and then filtered, 111.31- nitrogen, into a timeemecked flask. Five grams (0.3.2 mole) of cyclopromo was passed in. After one hour the solution was poured onto 300 g. of ice and 20 g. of sodium bicaroomto. Toe mtor lazmr 1:13 ccfiracted with three 50-011. portions of other, and the other lay?! were combined. The ether «(tract we wished with five 50-911. portions 01' 3.03 sodium hydra-213323. The other In: dried over mmosium sulfate. 33o residue MELW after razmal of the ether 0 2. dcetyl thlorato with 1,1-Dinstlur1cycloprogme A solution of acetyl perchlorate was prepared from 2.11 g. (0.2 mole) at 011m perclflorato, 200 1111. of nitrometimue and 17.2 g. (0.22 mole) of acetyl chloride as described in the preceding experimmt. 1,1-Dimcfivl- W (111.1; g., 0.2 mole) ms added to the solution, with stirring, at 0°. The mom was allowed to stand for one hour and then poured into 200 :1. of 5% sodium bicarbonate. Tho outer solution was extracted dth five 50-121. portions of ether. The other extracts were combined '4- .. . ‘ - ' n . ...- a . e. ' ‘ l . . .v . 4 A A ‘ l. .‘ M . g‘ ‘1 ' 5 fi - '\ d p . A. 0 7— - ’ ‘ I ~ . p ‘ ‘ . Q . s . ‘r ‘ ‘ k n d _ . t . i ‘ ' I . ‘ . .4 . ‘ r -. ~ A . . . . . : . . '- ,. ~ . . . A . ' .l . 4 . , -- _. . ~ ‘—. ‘ u . é ‘ t {'7 I 1 V . I) 1 . \ O u . .. .. . - I .. g ‘ A ‘ _ . . ,- . ,u . d . A ‘ ., .._ .. .' l ' - t. .\ t 5v 1 i ,9. and dried over macaw sol-fats. I'dgcn distilled, the other attracts did not yield any product. mm}: boiled above 103° (Ifltxmoo‘tlmw, 13.1). 100°). The last portion of distillate did, however, yield; derivative with 2,h<2.iuitroph . "ll‘yflraoblo which ml‘ood at 129430" and . mixed molting point. dctocmimtion with tho 2,1.«iinitr-ophom'lhydrazona of. 3,11-difi‘l3fl‘lyl.3¢ ponton-2-ono as prepared predowly give no doproosion. f—‘o‘“v ”oi-*to "A “M“: 99:599-103.!- I ‘ _ J ' ’5! 45-3 Ecru-U..- a“... {35.4 L; J u... ‘- l'nc method of Unfizoofor (56) was used for the chlorine analyses o: the 11:31.13 products. Tm goo-:33 of calm, cut into four or fivo pieces, was placed in o 2:30-1:11. Smdflct flask can‘a'zininz 35 m1. of 9955 iaoprowl . alcohol. A samplo of 0.10-0.30 g. of the compomxi being named no word and the solution was roflzmoi for ow to four houro. The moon sodium mo docorzpoood by cautiously cling moor wrong}: the condenser. Fifty milliliooro of unto-r one added, and the oolution noutralizod to occago rod paper Him 6 21 nitric acid. The chloride ion ma titratal by the Vollmrd not: ' The other olommml anolyooo ware done by 00113: liicroanalytical laboratories, Eackmsaok, 23m: Jot-coy, or micro-Tech. laboratories, Skokie, Illinois. I-iolting points wore dctmminod in a capillary in on affic iontly stirrod, electrically hoot-3d, oil bath uoing c flammtor calibrated aw o Bureau of Stzmdarcls thcc'momtor. Stem corrections were not mdo. Inimrod absorption spectra word run using a Perkin-Elmer, I-iodol 21 spectrophotometer. Tho ultraviolet 31.3mm were taken using 3 233cm, nodal BX recording opoctmylotommr . 61 23133323.} Several 0:me fonts 1mm pcrfornxxi to c ’etonuino idiotiwr the [‘r film‘oizotonoo 0 02,51 [I i R 0 C '- C - H H 'n 0.33 are found dircctly in tho acylotion of cyclopropcne, or another way are formal he; porno imiiroct path. Cm of those pocafinilitioo had already been tootod by Curtis (23). For moronic, it is cmcoivablo tint cyclo- propane cou..d be owlatod directly to an alkyl cyclopropyl kotono, tuck, on elbooqamt reaction with tom-311 cklcrido (in the presence of! alxuirnm clflorid a) mic-ht local. to t”: o observed Po and X-ohlorolcetono mime. Altzmugh ring wing to tho 9- (momr than 3’ -) cronmketona is an mflfltdy prospect, it mo novca'mclooo investigated by Curtis, mo 0 o 9 n /C:'zg ,C- 3:: PC}. R‘C {rcj'a-C"3-(31 R . C .. Cl o \ --- Rae-Cg 13'1" CH3 C?1a“03’=«a“ 12-3-0; ‘Cflfil treated nmropyl cyclopropfi l-rotono with olumimm chloride and rmh'cgon chloride in daloroform oolu‘eion for ten hours at 0°. The kotono won recovered in greater than 88;. yield and there mo no ovidmco for the formtion of any chlomlzotonoo. Thus, mad-or the conditions or the deflation reaction aligrl qm'lqarom’]. l-zetonos are stable 3 they fixmforc camwt be intozmodiatco m tiara foztmtioo of tho chloroicotonoo. .‘ --..- .0 Anoti'ier possibility in tint the F-chlorokotoneo are fornod by some tournament dancing mo conrso of tho acylation. O 0 1' n n / 1" 3.443330213533431 #- Iii-Cal}; E‘s-n crpcrimcnts closer-fled in this thesis indicate tint this postulnto for the mode of remain-ion of tire f-chloroicotonco is also incorrect. than S-c‘rzloro-Z-tpcntanono (tho ‘5’ wizlomlcotono from as otyl chlorido and cyclo- propane) was stirred, in amorofom solution at Col-3° for one hour, with a h-«i'old cocoons of an equimlzr mtzture of acetyl ctfloride and almnizmn clflnrida (12ml reprochzcing all of the acylation conditions, czzcopt for the mlopmmno) it we. recovra‘od unchanged in 80:: yield. more was no evidence for the formation of h—cfiflcro-B «notwl-Z-bu’mno (the P-chloro- kotono) or 3-mefi1y1-3 -buton-2-ono, its dohydrohalogmntinn prochct. Under those conditions, than, tho X «chlorokotonos do not rozmngo to the Edmonton‘s. On the promise that pmpa curing the acylntion (with cyclopromno present) some circumctomc on are gmcratod mach allow this rocrrangcmmt to occur, the acylation was carried out in tho presence of a rather large «paucity of initially awed X wiflnrokctone. The yield a: r-cmoroketone (or its dmmmtm procmct) ms momma, and the amount or ‘X-chlamko‘tono reamed comopomlod closely to the sum of the initially mod pm um czpact-ao to ho formd from the acylation. It is folt, thoroforc, that it is mi‘o to conclude that the P-chloro- ko’oonoa are not fonaod by roomngomont of the X wiflomko’wms, nor from 63 the any]. cyolopropyl kctonoe and rat‘ogon chloride, but are probably produced by some more direct process from the reactants. One can wavelets; about the possible nature of this process. For eagle, a comm my form mulch could cabeecpmm break dam by either of two paths to yield either the 9-- or the X-chloroketone. me my propose an intonndinte such as a 32.2mm type ammte consisting of 3 cycle-- propane ring between the ions of the acyloifloride-clmnimm chloride c0291»!!! 0 Wofnmarbonbommthecyclcmpeneflnxiithaddiflm of theimatothecito ottkmcleavagemfldlecdto the X-chleroketcm. . 0 ”:3 ‘ @ u o I ' l' 1/ 0“ ----—-~ R-C-CEIa-Cfia-CflaCl B \H \ . ,c : H p e . fix \ of $3.231 Homer, if more of a carbon-Lwdmgm bond rather than a. carbon- carbon bond occurred (such a situation could presumbly arise if the carbon-imam bonding electrons were located more auibfialy for -..-s. f': - z _ l O N f' | r' ‘ , ./ ‘ I l ‘ .1 . \ -1 “H . \ . .... y \ \H‘ \ l.’ 0 \. ...-— ' 'L' _‘r-'-.-' 0‘ n ‘ I \. ; 1 \ " \‘ / ‘I ‘. I ‘_,' ~ ’ v‘ ' ‘ , . g. 1 l 1 "1 . ’ . . - u n ‘ ' ' f.‘ Y . . ..1 v‘ » - - o .....- .- interaction with the attecidng ecylontm ion) 1911er by a concerted attack of the diaphcod proton and the aluminum tetrachloride ion, the B-chloroketone could be accented for. RC '0 R-Cao A: / ,3 ll /c:za / H C .r x g n / 0‘3 ...—...... {I / HH R-C-CJ ‘c’ \ B Q of 3,01 H’ \c’ ./ JH ~‘I'I 111.91. Such a mechanism, however, is difficult to accept because of the segueme muting that the proton displaced by the ncylonjmn ion take part in the rumor-:0 of a bond which was enable toward the ecyleting agent. At the present writing, the melamine of fomtion of the P-chloroketone is not yet clear. In order to both determine the direction of ring Opening in the ecyletion reaction and to farmer ezrplore the scope of the reaction, the ecyletion of several substituted cyclopropenea was studied. Ordinarily, additions to substituted cyclopropenoe follow l-ierlmmxikoi‘f'e rule. For; ecchle, the reaction of 1,1,2-wmoifi1ylcyclopr0pane with hydrOgen bromide fields 2-bmm-2,3-dimt‘vlimtnne (5'7). czza-czx\ / on, on, on, | /C\ 9 II“: -----b > OH «Br CH, CH3 (:11, H, Under certain circmnstmmcee, mammal etoric requirements my canoe non- E-iarkomflcoff ring opening. Thus, manure we trmefonoed to an olefin, \ \ I ‘ . \ \ ‘ s .' ‘ \ \ \ ‘ . i \ - I r '_ a . ' . n I I o I ‘ I ‘ ‘ i x. I. . y \ ’r I ‘C . 3'. 1‘ I . . .0: ... U I' . ‘ 7 _ - . . . ‘ ~ I ‘ . . l i I K I, I v F ‘ i I k x, ‘ r ' -‘ ’I \4 the 3th or thick: talented that the Met mxbstimted bond we broken, followed by mmdmin wt (53). CH; ,. CF.) «0 H31 ----9 .. or CH, ‘ CII3 , CH3 CH3 3" one 033 " 033 ’53: ,. 1,1-Divoethylcycloprme , prepared by methods described in the literetzme, reacted mootmy with me 1:]. complex of ecctyl chloride and altruistic chloride in cicororom at ~10 to 0°. A 59:5 yield of what appeared to be a single chlorolcetone was obtained. Deheloéemtion of this product with zinc in glacial ncetio acid gm 3,h-dimothyl-2dpentmne. Dehydra- helogemtion, by 10;: sodium carbonate gave 3,h-d$mt}wl-3-penten-2-one. negmmmomwn with 10;: sodium Imiroxide gave the m «2,9. unsaturated ketone plus 1 cyclobutenone derivntive (probably 2 ,3 ,3-trinethyl cyclo- bntanone) . The structure me than chm to be h-chloro-3 ,h-dimetlwl-Z- pentwuone. 3 Zn A A ens-cm - ca - c213 Hi6 V ' ' on, on, 3 “1 3 I CH, on, CH, CH; v or \‘ . . r: 4&2“! ’ 9 93 Cu: I 031.0. "’ we ) “‘3 This mom do” not correspond to any of the posaiblo X dchloro- ketonea «poem from 1,1-diimthyloyclopropono: 9 , ('31.. _ cafe-CH rem-(34:1, ‘ on; a 52am: 0733 :2 w cafe-orifc «- cum. ' fifla 01' the fi-chlomketonu. mien man be coated (in View of the promote obtainod trm cyclopropono itaoli‘) the most 11km one is that mien one observed: as fin mar reaction prochict. ‘ It corresponds to attack by acyl at one of the lawn!» pupa, with Wfl' of Wm to the other mthylonoc. . , f' 0 01:3 3 ‘I I , H --—-v- C33 - c «LI-CH - /Cl CH; . c I- 0 Cl"!3 Tun-tor of the hydrogen to the non mum position‘wild give emu O u / oil-c1: I 3 CH3 mm: is not rigorously excluded by the charm-id reactions or clfleroko'tom obtained (aims prototropiolrmmnganiant of the double bond wit. occur lo. a l'a0‘3. I I \ I . . . . o/v\ . . a . I \ .... o . . , x L ,s r _ . . r v I O .. C . ..h ...3 I ‘lll ...! i! n o .. .. t . F O u . § . a h ‘ .. , .4 r . V _ ... i V“ ‘ w . ., ‘ i . Q I _ .. a , i 'u. f s I ‘ a . ‘ v n. a. .‘Z i! 9‘ u .. l I n . ‘ .o I. l\ ._ ' , n if». u w . I ‘ 4“- , a \ ../ If! r I v v. u/ .\ v. 0Q \ v x J- h N) ..l ... 9 ..‘ \ ...L I' .. ,v r . 67 upon demlrchelogsmtion) . The etmctnre of the product ' we: established an the former P-chloroketone by synthesis. The reaction of thhyl-Z-bu‘aem with sooty]. chloride has been. reported to yield the name product (29). f3?” 3 (ins 9E3 (233000]. + 033-01—1-0\ 4:353“- 0330-03 - c-cx NY. on Vina $4.3 Repetition of this mtheeie give a. prettiet whose infrared epec‘ormo ma menthol with that of the product from 1,1-dimethylcyclopc‘opane. This conclnoively proves the structure of the product, but. use euggeeee en 31 - tive method by which it might be fenced: that 13, the LIME-cyl- cyclopropene migit isommize to 2methylc2-butene prior to ecylo’oion. This path we dictinctly ruled out for cyclopmpane itself, but comet be mlnded hm. An increase in refractive indm: of 1,1,2-trinotmrlcycloo promo ever clmaimn chloride has been attributed to both an isomerieation and polymerization (59). Other workers (60) report very rapid In! complete polymerization of 1,1-dimetbylcyclope‘opene in the presence of nlnninm bromide m at 60°, the reaction being complete within a. few nimtee. Manlexperimentewerc performedwitbthehopeofminingceme insigm awning the mechanism of this reaction. 1,1-Dimtby1cyclo- ' propane we placed in chloroform containing oluzznimn chloride at 0° for one hour. neither the mlopmmrl compomxi nor an isomrizdtinn Mot were recovered. Instead- the cm'iqmpene me converted to a polymeric oil. khan the acyletion we carried out. in the presence of mass ,l-clhnthylcwloyropmo none of th. . crease 1—r> .13 rocavorcd, but c3733.? cod to be comcrtod to t: 10 palms: c :33. coir . The acyla ..ion me also carried out at -§O° and by invaooo 51:1." tion (ti-1o acylation solution is added to a clflorofom solution of the cyclopropane) . In both cases the yield of kotono me roducod (5:3) while the mat of polymeric product increased. ...-coo exporin'mte 1113:“ roots that the acylation of 1,141.wa - cyclopmoane is accorzpanicvi by a cor-rowing reaction which Woes the polymer. Pcrluoo milder conditions (3.3. a weaker Louie mid camlyct) who" ’ produce a. higwr yield of kotono. The use of sulfur «11-151610 as oolvmzt 111.11 a Lewis eo‘ ‘- 1.11011 as o mimic ciao: 11;. o could woof-11y provide an icloal ayotmn for this Faction. 3:111'111' 13.02.1119 has been 81101411 to be an awellent solvent for t‘xlo two of: reaction (.511) . The nmt substituted csmlop‘oopane whose acylation nae hrveetigated was cycloproznrl chloride, pragmrvxl by the irradiation of a. mix farce of cgolopropane am! clflorino. It gave a clig‘xtly momnmic mac ..ion w... 1111 a 1:1 oomplm: of acct-{1 clflorido-clmzirnm chloride. Attempts to parii‘y the product from this react ion by distillation at 3 mm. mrcury gave doc'omzmsition. The structure of the initial promct was therefore not establiebed, but treatment vi ‘1 10:1? sodium bicarbonate converted it to its da‘mlrohalogmation produc v, a diotillable chlorokotono, in an over-- all yield of 2333. The ultraviolet and inficred aLaorption spectra. of this prochzct were consist-ant with on (1,?” dmbotimtod-«t; «meatumtod ketone. Reduction with maimgon over platimm cave 34m't‘nrl-2-butaml. This establlo. co the carbon 61.301.31.071 1"." m Chg 71- '? R’/ 6513 - C4: . D'I \ C" ......... w:1. 8:35; farfi-zar, aim-m tint the mt did not result from normal mum of new}. chloride to the mlampam ring, which would rave given n-progyl , raihm‘ than isapmmrlmflvlcarb incl. Lifiinn mama ism-1:323 reduced the katono to a chlarina—contaimm m‘awatod alcohol , the fluorine of mic}; ave no precipitate #353: 5'3 alcoholic silver nimufia'. m1 ciflorixla , under similar cmiitions , give an 1mm precipitate a! silver crusade. These facts establish the alcohol as 05? CH5]. .- '- // C“; . Cl: - C \ CT!“ 0 C2101 _ || // and the ka‘uam ca Gris - C - C . . \ .313 T313 possible prochmts of €19 original variation, 391:: mixing only those possibilities mich walla give the rearrangmt prochzct (1.9., 9-ctflmvkefones), m nhom in the scheme: ‘5 7O (a) Q C” '"1 "" a - a. J Cf; . ... . 3 Jr. - / a (hawk Cl (Mirna, Giza‘C-C/I‘I —-">‘ ' 1. CEI.;.-gw"/ (WV ‘czzgm. ° ‘cz-{gzl (b) (a)? ....+ “3'" M 9 C333 JV“! 3 (I... A. 4 0-:‘3é4< _ h. V..." \ c3530). Cl The only path leading eocclnsively to the observed product is (a) which, like 1210 1,1-diaetZzylcyoloprop'me reaction, involves attack at the ant‘rvlme and ignition of the manger: to the loaet substituted of the mining“ carbon atoms. Path (b), alti'xough expected to lead to two m‘mtod ketones, one of mic}: has an ”lie cmorino, is not however rigorously acoluded, for one of the two da‘zfimhologmntion products mig'zt {redemmtco Prior ram-angmmt oi‘ cyclopropyl chloride to nllyl chloride cannot lead to the observed product. Roamnmmt to the viz-5'1 chloride , followed by addition of aoetyl chloride as shown, might be an alternative, thong: unlikely, path to the observed product. a}! I tea-Cl -- czxaczeacI-Iol ------9- CH3 E! «- c231. on. -o H. J » Q‘ II 3-": .3- ‘1'“- I ‘Iii ‘ 1‘ ..u {as to s ‘ Ill!- I‘ll-VIVIIII. . (.139: .1 n ‘04 1.1"! . . Vu-ug,.'¢r 71 .13 possible my to decide batman the altarmtive otruotm‘eo for t..- o initial or Ltion product maid be to study the reaction or cycloc - 2y]. chloriie nth sooty—l bromide) the diholonotono product wild be oitizw a E-brom-o-chloroizoi no or a P-bromoq? -chlorokotono. Cl 0 03.31‘ 0 BrCIr ‘31 ' {1%. “J. 03 _ 4. Ila-0032'“ R-C-cb cc}! 3 or Hut) -0513. 1 CH. —' CI}. Loivhmfinbmtion of the form would give o,{.’ «unsaturated ketoneo containing bromine but free of chlorine, warms the latter would yield 5 torture of kotonoe containmg bromine and chlorine. 0 CflaBr O CID:- 0 03.83: R-C-g - CH, ----o- R-C . CuC‘iI3 4 R-C - C I CH, 1 O ClCIBr (3 Cit“: 9 3131' l R-«i‘. ~c-cz23—--. 9-0 -0 «HIE:a +R-C-C-Ciia H 'mo r4“: :tion of cycle; arogvyl cifloride wi ..h acetyl chloride load to on momma. mfldmtii‘iod mot, b.p.‘ 62-65”, (ammmly so yield). The infierod absorption cpootnm of this anteriol ohmd tw carborurl penfiifl. Attempts to 3mm the: constituents by distillation wore not uocoeoml. . 1,1-Diohlorocyclopromno, obtained on o. bar-product from the prepara- tion of oycbpromrl chloride, me o. flat-ed only with difficulty. In order to cause I reaction it was necessary to heat the oidorofom solution to refhm for five to six Indra. The unstable product, vanish ma obtained 72 in 821111 yiold, gave an Lnfimod absorption Spectrum which indicated the momma of an unsaturated kotono. This material we not hmstizotod mrfiwcr. The recovery of 6733 of umoochod dicidorocyclopropono oftor one hour at 50° hu'thor testifies to slow reaction in this case. Such slow reaction with a big-fly nomtivoly substituted cyclom-opano suggests that the rate is determined by olectrcphilio attack (pi-ammo]: by ccyl carbonmm ion) . In order to dotamino the offoct or an mmtic mbstitumt on tho cyclopropane ring, the deflation of phozn'lcycloprogmo was carried out. Phoevlcyclopropono Ina prqam‘od by distillation of the reaction mixture mom cmmmmamrde and romaine 2min . This mm m readily ocylotod at 0° to yield not or a product free of chlorine. Tho W absorption cpoctmm of this mtoriol ma conoiotont with that for a dit- sutotitutod bemono ring. 4 Oxidation with chronic acid gave torophthalic acid. The halofom motion with bromine in 3015 sodium hydroxide load to p-cyclopo'opylbonzoic acid. It was thus film that the product as p-cyclopropylacotophomno . l O o I! “"31 ll ' 033001 . m -—“-’--3--9 CHa-C- Tho rel-mum or this promot indicatoa that the phem’l ring is attacked in preference to the cyclopmpano ring: presumably the cyclopropnno ring acts as an electron donor activating the hormone ring, whm'eaa the «I effect of the phaurl group dooctivotos tho cyclopropano ring. 73 A small amount (10,?) of the protest obtained me a hicjxor boiling liquid mice did not crystallize, but rower famed a glaee when frozen. This mteriel had an tutored absorption spectrum characteristic of an acotophonone. The refractive indm: indicated that the material was a mixture and atteuote to isolate ite components by distillation were un- aucceesml. The stator of this reaction by Curtis and Bart (23,224) was limited to the use of carboowlic acid chlorides conminfmg only hydrocarbon subotitnenta (e.g. boar. oyl chloride, propiom'l chloride, cycloprogimc- carbczvl chloride). In order to farther explore the scope and litigation: or this reaction several comments with corpmmde not in this category were studied. Chlm'oocoWl chloride reacted readily with cyclOpropane to yield . 33' of c mixture of chloroketonoe. This mteriol could not be fractionally distilled ct 3 no. of mercury pressure due to decomposition. It was therefore mm with 10:: sodium bicarbonate to selectively dehydro- imlpcemte the P-chlomkctone. The chicroketonee obtained after this treatment m readily eogxratod into two distinct fractions by distil- lation. Toe low-boiling product bod the formla 053,001 and me reduced with hydrogm and Itiney nickel to yield Bwthyl-Z-butmone. Zinc and acetic acid reduced this product to Smotmrl-B-buten-a-ol, mich we qnficoeized MWently as show in the scheme. . | ‘ . - ‘3 . .. . I ' ‘ I ‘ * a, r . . o . ‘ ...- \ ,. r h . ..- 4 " f u . ‘ H .e v— ‘ . r ‘ k ‘ V , fl "' _- s - a 711 r ‘0' /C;13 ii ' 2‘3": '0'“ o I: C" u // a a ClC‘ia-C-ac\ ...—.... on, on on, 7.»: I // _‘-" (3 CZE3-CH-C\ ‘O b 1 ’Y “3 Lula. O 0 401i. mummy-<23, 939-» -c «0’: C33 The s'trucmre of the lover be fling fraction was time 81 10m to be l-cI dero- Bar-win; l-S-butm': e-2-or1e. in at" wept to prepare this common by the motion of diazoznot‘zone with 2-chloromtbvlpmpiomrl chloride did not give clear-out results. Analysis of the maize: boilmg product agreed with flat calculated for I. dichlmpentanem. 1,5-Dichloropentanone, prepared via the mtioo of h-chlorobumlchloride and diezomefixane m m to be the some a thin predict by its new absorption spectral md 2,11-dinitro- phavmydnsom dermuve. O 0 C141: .,-cz: roars-C1 —-£-I> 01-02: array-cc...“ M, ‘3 01014311, C21,, "' «31321 9 I}. It is clear than that here too, the acylation of cyclopromne gave both merged and noml product. ‘.V!‘I‘-a. III I '53... Ail!” 1 O O H II \ 1 5:3 n c. CL11§£II/Cl-n\.1 " \ _, ca, Two other types or commute often used in Frieda-Crafts mtione are 0.123% and Miami halides. 3.1:: halides are brown to react with claims to yield both an addition pro