FREE RADICAL REACTIONS OF COMPOUMS CONTAINING “IIHE CYCLOPROPANE AND OTHER ALICYCLIC RINGS Thesis Ior the bum oI Ph. D. MICHIGAN STATE UNIVERSITY Donald Paul Wyman 1957 ,. r . 4 l“ 11mg“, GK)! NIC'rIICM‘I STATE UI‘HVERSITY 0F AGRECL’LIL’i-IL 9:.L AJPLLLU '_s:,;;£uCE FACT LAN ’5: .V C- . MlbnluAIV |fi \7‘ FIT: 15.311311. 311312111233 0? CfiifLUTE'z‘B 833231331316 Tli'v'i Cinla'l‘iiififiifi Mil} (7153711 ALICI‘JLIC ERIE-3&5 3.? Ronald Paul Hymn Submitted to the Sc? .001 of Advanced Grains“ Studies or E-zicizigan Stat»! University of Agricml’mro 1nd Applied Edema in partial Milka-ant 01' than ”claimants for the degree of 206133 CF P25103933! Dcpartmoat of CEIWW 1:} L7 r7“ mam. :27 $1137.13 01" or). van-13:3 cmmmznzo m: exam: :7: m 01:73 m 2.3.1:: mm 30111161 Paul k‘ymn £3 ammac'r Submttod to the Scztml or Advanced Graduate Studies of modem: Shh Univmnity of Agriculture und Applied: 801ch in portal mummt or the ”quiz-mu for the degree of M710?! 0? PHILQSCPTII Eapnrtmt of Chemistry I'm 195? Ammod II II [I I1 l t 'z'aaq- - flunk. 1- 4%“ Q‘- 1'2:io 57.127333 31’ t; :13 1:37 2.32.- 3313: ml '33 3:23.22: 3:333 .2. -333. 2.3:: :1me 1'23 33‘: 3213: 35-31.. wpfl am: egm 2:337:13“? 27 '1- 3.3 mum. In W3? 23 :13 this 322.2 1:3 be 3313 33 3:31:12. mt. 2:21:23..." “-7" if». um]. dam-31.331.51.13: {23157272.22’3232‘123 , p3m:.;.’.::ii~:3ll It? "-132“: 3:743... 1:332:23 «demarcation 9373.157: t2 .0 (2:35:137‘33371 , c;313:217:-p;‘l¢32‘bi:gr1, 3-3 3:22.11 (.3 12:3 33313232.: 1.71 1.7373371 37313 3:71 5:32 37733311742713.1177]. 1.7737“ 7’7 c; ..-... 2.3713332: 2.sz mfg-1&1: m pmmfi 3:32 cirwraa-‘r . 3236,1531: was 3.13: mated why 3:; a p 3%:23213 1 32.13313331233 3.“: 733133: 33713135233932» 33393223133: “firecaztm, 33:2 7:33 .2333 933312.13; 633732721332. .--.9 03132717132133: at 1373377713“:- mawra :13]. 3:2 2-31.!3139. “7:27.11- 1.331323772333233, wt: .3? tam t a 31:3: 33.. (12.332; 7171313337771 "1.2.72.1 32:13:71,730. 12:3 613%th 31' 31mLM...m:-: 17-133. 3:33 waits..." ‘ 1:: 22:3 {321731.331 of 1-3.7‘13'77377'1- us: 133.. 3.232134. 3312.13 3.2: 234175221333 01' t 333 1331133 3:23 3:53.33; . 2‘33 minefi- nnfi. rates 3! :5 3333933231331 .231- 2.1.3 .1 3.33.1: 3-3 mm 63332731332. 5.11 c: 1.2-3 :7 .327 3. 3 212m mm :33? farm: in 611323 smut... in cum to 373351371693. 72’ .7 3W 3217173 11.33% 312...: 2...: 2.2.33. 12:3 91-11mm pmtimts m (22:33}. in all 3333: 231% cm W (33:33:; 61:32:33, 132234 313.3175...” 0 (2:31), m! 1333333333212: 3! 33333 (112;?) 3.372331! (’2 .333 '7}. 12.3333 31‘ 77333333 33373 9:32.233 3.2, 3.32 22-33332-2133332; .3233 was £333.33 in 1:37:53 but 332333231333 wfititias. 2:27.33: 5?. m Doc?” 1.2.3 11? 0523: m 22:3 33.33: gum-7:331. (33.2}. 3:: 1:3 2:31 933 323W}. 1:: 1211 mm ) 94‘: of €19 93273232353 m 3:363:3333-‘12 11:22" inn-.2 2-. 3332323122352, 133 57.32-13.90;ng 111233,??? . mat-33:21:: 0323713! 3.! 2.2.3 3373323323 W33 8575133813323 £3!- ccn: 7 372.333. 2223 13133133 273233 31‘ 3323733372213: 3! 2.1:: 33277133! pmziziaa at .303 in m tamizlarlw 1.23.773: :2: : o,::_¢.: 7‘l‘t“.i. ‘ ”431 nah—l J3, ‘ .1 o 8:93 C. 6035 ’3. ‘ L“ C: 3 .a c. 2.73 C* ’30:: £3 20.: a, 73.2 11172333 2232130371 93:73:31,223 bad a 1:33.223 32‘ 1.0. 3-2323. were (293333111133 at 333323.]. 23:33am?“ and. on 3273;212:323 $133133. 1'? :3 33317232131: 33337577133 for 1.11 2.2:! pawl-31.398 3133332. hiscyalepmpanefomrl and 2313:7313-3133:133- ncetyl 9317373133. V3170 25: t 1 2:11:331317139 pm 3313. 272:3 activatim «norm for bimyclcpmpanaromd pend-33 an 2? 11133313313: per 331:, W 12732 for biocy'clopmganamml pmzida m 3111;? 22 1711333133133 per 3313. The 3-32.33 , 12273223328, 332.3331 33 am”: 022257313133 of animation 93:79 311 33735132332 31:71 n 3331733133. 13.2.1337: 1331331322 23:: fort-232.133: of an wry). 1131331 no one of 2.33 rate (232317323233 ”we. 2223 37333223333 mm: of 1&1. qmlapmggdmxfilwl msfiml #va m be lgymciama . I-atmin in 1510 Qmmpmyl m3, ta 1!. 1mm but still Lmorwrh mag-21%, in the gammy). mfiiml cm: accemt far 1.7.29.2: aim: mm of {arr-mum. Cycloprowl 10:31am mo prap raw} rm: tan first tim tram tilt-9 amoro- Iium or bmyclcgmremxl gmflm in the preamco a! tafim. It m net ham mm panama ta mum $21.9 mm by cfisyhcvwmxz macaw. A new, cmwambly tfiwmi, Ignti‘wuia or $0139qu *1- Mcmzahyfie based or: wish-tic C—flffifil‘fiigmtim of the alco:"-;ol ma tents-v.33. Ira-a pragaratim an“ 3 ,Z-c;iayclcgtrowbrmgma-l ass-.3 we afglntéufifl by a trauma of matinm star-tang with die-3:21:39: "3-31 mums. mega-lon- propyl km as 3130 cam Wad to cyalagmpyl cwloyrm rear}: madman using hWrapmaz-‘acatio midi. award other new cfilwp :0;an- confiining Cori vativm m {maxi-793. . TAKE G1“ {31223323213 P356 r’mrwr‘" ufiL-wov a~vh¢ocooooooooooooooooooooooootoooqcoooooocoo¢ouo cocoon. ”'9 1-“er W414..L..u.31uooo.otoc¢agcoononcooooooooooooncooacooooooooonoun. I. FmigmtalaooooocoooococoooooOQOOouom-oo «10.000000000000900 A. 623.0th or fiy'ctrocarbmn Containing 3 Cyclo- mm Ring....u..u..uuu..uuuouuuuuu Pmtim Of Isomvylcyclopmgnnouuuuuuu. (I) Inapzvp'juienemlonic Esteroooooooooooooooo. b) Impmmrhmlanic E'émooooooooooo0009000.... 0) 2'MWW’39W133'K110100000090000000coo id; 1.3dé11b1‘0m4‘18091'OP'J’I-9WMOOOOQQOcoocoo. a Impmpylayclopropmeuu.«announce... cram-mum of Iaoympylcyclopropmo..uuuuuu Mam-d Reagemt from the Precinct. 0! Chlorination 0f Iwmdmlm‘IEDCUQQooooooouooooooooooooo 301mm:- of the Product of (Imam of IIWNWIml-Opmfmmocoooooooooooooooocoocoo... Chlorimtim 0f Imatane..nuuuouuno“....u PMWJWE’M’I Chloridioocoooooooooooooo Chlorimtion Of 2,3-Mmatnylmmuuuu«an... mCflWfimnmoooooooooooooounoooooooooono. Chlorinution Of inWl—WMOOOOOOOOOOOOOO. Reaction of the Profiuct of Chlormuon of Bicyclopmpylmthano With Humiliaooooooooeooo mum of the Product of Chlorination o: mmwmmouoanncutnc"coo-0000.0". B. Pram-tuna an: Bocozspuiuon at cm mamas A631 PWidalooocaaoooooooooO¢outooouaocoooooooooo Premntion of we acquired W119 Adan“... Cyclopmumx‘boxync Adriannuuuuuuou... CycloE'xaptanmfiomvlia AcidOCOOOOOOOOOOQOOOI0"..4OQO (Q) mummlo.covenants-000.00.00.00.-no... ébg Cycloheptyl Bl‘Omeocotoooooococooooocootooo O Cycloheytanaoarbowlio ACMQoOOoo-00000000000 03001516 AC1dOOOOOO-OOOOOGOOCOOOO000.0090. (I Cyclo‘in‘ommloucooonoooooo00.030.00.00 b WPWWWGEWooaoooooocoooooooooo c Cycbpropsnmetio Mucoooooooooooooooooooo V11 1 7 23.51155 pa '63.:35 5 22 ME (3' C(HE‘JI‘S c Cmtimzad Page " unaccetio Leidooo¢000Iuooooooocoo-00000.0: 29 I. CYCIOPMchfll‘bmlcoooo.oooooocoto...o.coco 29 b CYOIODW‘WWW]. WdCoooooooto-oooococ 29 0) Cyclopontmcatio ‘cmooocmuoooocoo-ooooooo :0 herniation 0f €13 11.6543 ‘3}WW000000000000000000 33 Cyclopmpanmarbom'l 031101'16‘9...npoooocmaoocooooooo 3O Cyclopmmrbonyl 0311033163...00.090000000050000. 31 Pmmtion Of W18? Acid C’kflbfléflfloooouocooooooooo 31 Propantion or £30 liiacyl I‘deaooootoooo.ooooo 31 BiwfilOWOMfOI‘F—Xj'l Pamfiidcc0.000000000000000... 33 Biocyolom‘opamacetyl Peroxidflooooocooocaoooooococo 3’4 Other Acyl P61013161”.coo...ova-0.0000000000000000.o 3L3 Preparation Of Sarah: Efltafl00ocooonooooooooocoooo 3,) We NW1 Cychmpunmarbmqlabaunnu"no... 36 fl ”1:130”meth AcmoQQOOOOOQOOOOOCDOO 3;) b Cyclopmrryl Cyclom'opmomrbomhtouuu... 3", Cycloprowlcarbimrl Cyclopropanmetatenuuuuu 33 (3'01!)th CfibhfiWWhtaonoooooooootono... 39 Cyolphmg'lmrbhvl Cyclchmwancmu...nun..." 39 thl WMWOOOGronno000000000000090.000000... 39 II. App-Lam for Product: and Kinetic! of Winn or V8110“. #671 Pmfidagooooouc.0000...oooocmooocoooocotogo LO thtitatlvo Betamfimtim Of Mat-00.000000000- Producto from the tacowoaition of Biomloc pmmnofoml PWOocontooocoooloou000000.000 Products of Lbcomition o: Eiscyclopmm- 5i: ‘0“?). PWQOOOOOOOOOOQOOOOOOOOOQQOOOOOOOOOOO 1&5 Decomposition of Biscyclapromnefom'l I’m-oxide 113 $310 PIPES-£31100 0: 106.1136 and Wtwoooauooaoooooooo 5:1 titration of Becomition 01‘ Various Aayl Pwuo-OOiOOOOOOO’OO0000.000.0000000000000... 51 III. alumna”...unnuuuuuuuuu"unnuuu 52 1. auction: of $15910 Wm. Derivativu........u S2 Cychpmmd 106.150.00.000...oooooocoooococoon-0b... 52 Reaction of (mumpyl Iodide with NRWouooc 52 Cmic’ation of B-Syulepmmmoeuml with POWELL“? pmmmoooooooaoacoooooooocooaouo 53 CYClflpNWM-Wfi’fltiiotoooonowuvoooadooooococo 54 2. Attempted Preparation of Dir-ratlvlcyoloprogyla mm]. Chloridfiaooeooooooooococoa-oooounoooooooo. ‘5} viii. ma W cm '- Contkmed Page Reaction of Phosy‘wr us Trichlarida with lantha- GVCIUPPOFylcarbinolooa...c000...00¢oaoooooo¢oooo 7115313181131 Phosp'ziiw...oc000000.000...oo00000000.... auction of Mgr-mud Phoapzzita with Benzyl mamas with Ettmiylcyclopropylmmol. . . .' . o . 30 RGECtiOnC from Licycloprcpyl Ketono......o.o.......... 1,1‘LWW‘OID'1933W19118000 «00...... 000.000.0000.. Proof of Structure of 1,1£:icyciopropyleflvlma. . . . Ethyl Berta , bamflcychpmpyl-bamotqdmm. pmpionateoo9000.09.cocooooooooocoo-00000000000. mm beta , bate-(iicy'clopmpylncrylato. . . . . u u . . . . 3'3 LiCyUIOPTUP§1»A1131'5130501oodocouo000000000000 3,J-iicycloprcpylprcpanol...o...o..oo.o.o.......o.. 3,3afliqyclaprOpylprcpgiacetato....ooo......-.o..... 3,3'iLv165’Clflyl'Op3Q-‘1fl3mpaflaooo00cson-00000booooooo~ Attempt“ Pmmmticn or bicmlopropyl Glycidio “W........‘...OOOO.‘UCOQOQOCCOCQO00.......... Situation of Per‘ammoio acid with 1.1-Cicyclo-r progdothylmauuuuan..."..unu......uu BISCUCSIwuuuonunuunun..."nun-«noun."noun... A. ho. Radical Chlamums....uuunu..."nun......... B. Gnu-1 Wmtim Regarding the mmum a: [my]. PMMoocococoa-000.09.00.00...outocoocuoctooocoocooo c. mum and PM“. of W Any). Emmanuu. D. PM of the Decomposition of Sana {they}. ?m'oxidea...... E. ninetie- or the Bacomposition of. Various icy]. Parcxiczal...u F. PW Bantam.“ for tho Dmomoaitian of the Variant \‘1V‘l, V13? '1 V1 .‘ \ ‘31 ‘._a ‘l :1 K. ax U1 U ' '. U'L‘UIVIV‘I \‘3 (D " -J‘\ [N ‘\ (‘2 E"; m H 62 72 83 8’4 92 Am Parofidfloooocoooooouuooooccoooocootovo«unnuuooo 1334. 0. MW Ewan-cocoooooo-oooootoooootoooogowuoo 111 :2; '3 3 SUI-n“ ".Ycooooooooooocoo-cocoon.too...on00.00.000.000...oooocoaoooou 114 Lm’fims CWOCOOOOOOOOOOO.OOOOIOOODOOCOO.OOOOCOOOOOOQOCCOOOOII n7 WEE-EHOOOOIOCOOIOOOOOIOOQOQO.0....O’OOOOOOOOOOOOOOOOOOOODCOOI... m — .fl'" _.... ‘ ME LIST 0? 3&3? 1. momma ?rocso,©cxa-——~ cziz-czz-mro-c-czza 1210 Win“ W1 (33330211111: 10:3, 12 formed, an produced "111mm an! arranged radii: to 1213 um. carboninn ion. Cyclo- prowl arthritic 1. than u inert toward both 531 an: 3152 displacazmtl u chbrobmsmo (2). Th. difficulty in forming a positive ion with $210 crux-goons Wimbonatommmucribedto 14mm (3). Th“ 1., mm mm 1| (flanged rm 3; (neutral molecule) to up' («than ion), tho 1mm]. strain 1: imreaaaé. A poaaiblo mm of thin W in drain 1. given by the diffmaco batman the m 19.310. in tin two men: 1.... (120°«1o°)-(109.:,°-aa°) or 103°. ' Pm of thin thuin dull. 321th an maiytion of thin cm- W in It” radicals. The" is conflicting infatuation 1n the 11mm about cyclwmpyl radial” War certain 01mm” they can to ninth: their identity, more“ under other: they my W to. 1.11:1 radicals. The photocherdeel Wtinn at cycloprepene (h) proceeded with- out “tangent to yield cyclopmpyl chloride at the min product, alone with lectu- emmtl of dichloro amends. C]. e 01.4—1- Cle 0 -C1 Cl C]. Alto, flu. and 5311th- (E) tome {but the vapor phase nitration of W me nitrocyclomopanec firm" The Malta reaction on unva- czmlopmpenecarbwhte (-3) yielded W mde . We CO‘Ag m9 Br O 00‘ 9 Agflr W :11 of thus rotation meet! vie cyclcpropyl free radios]... Q: the other head, We reaction! which my involve rearrange- mat of eyelapropyl adieu: !m'e been reported. m, it in claim tht the Kalb. electron!” of petunia cycloprapexmrbem-lete ave marl mlmmwbmhto (7)! [>eogc 4-. [>—ca.-czz,-c:bczza o ca,‘ In. W at methyl cyclcprawl ketone (8) also yielded products in fish the eyelepromm ring I'M W. PEiOTQISm wmm 3 mm mm 2mg (8) Product Quantum Yield 509 M _fi : m_*__v:___;jfl___ :1... o CE{3-¢I:CI€-3-(;'E!3 0'31 0.0 0.05 Chg-czzrca-CE. 0.021 0 Chg-awn, 0.05 Dug-Gum Chan-(:3, 0.038? on. _ 0.0032; 81:91:23. 0.01:2 czzfcgz-c::.-czi,-czbcgt, c.0033 Wm 0.000 ._ w ; .L A —~ 3...... W ketonu when photomed cleave betwem the carbonyl carbon etaemdmotwenlmmpe. memmpmdmttmmtml eyelepmpyl km in nethyi mew). ketone, inch 9mm}: me from apt-fins of the eyelapmpme ring at the guitar: process. Some mm. Welding didoccur, however, givmgriutofhemprmiuctl “Inflatable. mwnmtmnkvtethepmfleMer of mm mien can be ascribed to ally). wile-ell (1.0., 1mm, W and cm) and the essential flame of promote directly derived Iran t W]. redial (1.9., cycloprOpane, mthylcycbc pm. dicyclopropyl). _ To main. the mm of cyclopmpyl radicals euro directly, the dbeyl puma: o! cycleprepemeerbmlie acid In prepared, and the kinetic. and products of decomposition were flushed. For W, Wdumiehvouldyleld highereycloellqlndimllmreeleepwpered and em. The restate m. reported in thin tho-1|. ' In contrast with the We with man eyelapropyl eerbanixm Lampmducod'utn- rumlgwmammmnms tumieh WWW]. We: teal. Shah mu huh hem etudied utmlhelyby Robert. (9). Win (9) and othere (n). mu type or in u .011: toned, end :- mama by miserable resonance my. 0 Q 4. 4: i T CI. 65. 1* ”etc. § mmlemmar-mmxum, lime emu-1 (12) shoved tat command: mieh lead to each ion: col-mm. extreme]: midi-y. Burungenmtl occurjn certain of these mm. For maple, WWW, nth nitrous acid, given both mime-minutiae]. end cyclobutenol. A {at mine of reaction- Ihich my proceed via. WMWI free Micah have been reported. The tree radical chlorination of ”@2710qu yielded e We of products which included olefine, [>-c:z, o 61. ---s- D—cnfi e cztfczz£3134rzacl (13) [>aCE}, a» Cl. our D-Cfifil 9 7 (1h) ”charts 12de that the allyleerbirvl chloride we prcruucrai by his . of the cyulapmm'laerbiwl free radical. DICK.“ W CIEfCIEc-Clia-Cigo Ln indioetim or the magma]. stability of e eyntee mum e- WW redial an observed by Orm-buger end about: (15’) in a study of the decommitim rate: of several encyclie amnituted m-bimitrnee. 3:3, $31, «EH3 M's-meats ----- 23-9- «H. w 3.: cm The ease iith $23.63: the cyclopropyl (2::sz deco-quasar! has been sun-lbw (15) ta resume etabilizetim of the radical producem F”: . .0313 r 3 , N n O Ion—9 C De I . [\ t can / ' ' 6 12.2ng 2 1.13 mm Cr!“ LJJTFLXSITI’E OF (fidgwflv). (153) .1 _ ‘ LA R o eyelo knees I 10 80° S. w A “w. :w“ _. _._.._ w w w w— _ “‘ M w —— ‘4“ c, 3.3 C‘ 1.551 C, 1.30 c, 2.2? 1mm}. 1.03 W M ...... ‘ “ _. 1w ... w w w W ‘ A “ “u”: T __ ‘1‘: In thin thesis, tun approachoe to the emotion of mimomrl- whim tree Mimi. we need. m- ohlorimtion of certain hyo'ro. urban! (WMoyohpz-orgmne and dioyohpropylmetfm) which would be expected to give inmates with one or tm cardamom rings on the cum bearing the odd electron me meetigated. Alec, éhcyl madden Ihioh would give the cyclopropyloerhimrl and other cycloenq'l-b W1 radians were momma, and the tzineticl mo productl or their mwtim m mama. 50m miscellaneous traction: m'olving @010me wwie are the recorded and discussed in the last part of the theeie. ”.9". own... at“ uni-"- t-hfil-OL A . fibrimtim of timirecarbom Emu-fining a C‘mlepz‘ozxene $ng IsompyliWe ester 13! prepare: according to the procedms of Gaindand Quin (1:5) and Cope as; zhncoek (1?). In I tcvieal prepemtion, a 3-1. mam-nee the}: equ W with s reflux comm was charged '1"! 730 g. (31.83 moles) of nevi 22311021359, 720 g. (7.15 melee) of acetic new, 60 a. of mostly need sine ensues, and 5530 3. (3.1.2; melee) otteetom. Thedxtnromreflmcedferlmhm,dtaruh1eh1tm cooled end poured into three liters of new. mu aqueou- Mm was mated with three 3:2«1. portiene er beware. The embined beware mm m dried over calcite: 0321 (in (gamma) and the tmztxn-e as ten distillec‘. W trough a 13-inch Z’igrm‘: column to rewve the between. Frectiemtiee cf the resie’ml black mum firm@ a 15-inch clean hence peeked jacketed comm: yielded 623 a. (53.537) of 130mm].- mmemlonic ester, b.p. 103-127" at 5 1:23., n35 1.31.73. (2:) Icemmkmlenie Ester c" C: x n 3' .. _ vault ha rtav/ / «A $4\ - '3 H *1 CH; CE. 3»; a . “terms to me guess he; mpylidemeaalezfie ester at. ream mm and um utmsphemn of pressure with Kenny nickel catalyst Mme-M111. Ems-er, at a Maize: tert‘mmn am} pmomm, the Wm 01' twiregm prone-2m} mom-11y are: remaily. In e tan-tee]. preparation, a fatml. ugh pressure Wimmtim m an alleged with 300 g. (1.5 moles) of ieoprepylmmelenie eater and Wm]: 23 3. 01‘ away nickel catalyst. M. a. taepmtnre of 130° the prom fell meta: free on initial value or 830- pounfi. per mm inch to 55:10 peenfio per ammo inch in I. period: of 1.5 been. After reg-awe]. or tT-z‘aa catalyst by fumeum, were an obtained 298 g. (98;) at mpmpylmlmie eater, hp. 103° at 133’ m... 21?): 1.1.133. (e) 2~Impylpmpam4fiddel W '3 .4" C4;.\ a- ‘1’ /63-a4'a / {ii-mi\ on, mace kinemjlprepamdfidiol In W families the prececiure eagleyed by fines, mm, and Embieff (113-). A 2-1. three-«naked remi-bettmed nae equippfl with resin em- eeam, W. stirrer, and c‘ireppmg W m aim-gee with 31 g. (9.793 salad of utfiiam 31mm mama. and 500 ml. of nfi'xyirms «than Thorn no men need 1151 a. (0.5 mele- ) of WW altar, W, with etirrmg ever 5 period of: time hours. Tm melon Wmmummrmhwdwwmmmmlm. M the cadet this time, the firemen (sealed neumhnthud 3.25:1. etuwrenemdbymnw of tee cmmmoumfimw new a period of two be: "e . Separe'ehn or the (1101 from the matter: W by 12mm esvztmceim preeeziures peeved: meetisfactm’y (me to the femtion or emblem and the amiable aewility of. the 621.01 in mm. mass diffimltim were cinmmmtxed by the wee of liqum-llquid attractive... The rmctien mlx‘em‘e described above was «dz-acted in I tingle stage liqzid -11qe5.:3 animator with ether for time man‘s . After we}. of the fixer ‘ 3:32, distillation yielfied 1:? g. (70123) of 2W1prozme-lfi-diol, b.p. 133-131” at 13: m... I»? 1.1330. (6.) 1,3-é‘gibrozm-eropylpx-0pmm (:33 leaf}:- _ >CZI-CH\ e223 3:339” lfiisibmaaé deoprom'lpmpene mu pr:3;mm:1 by the proceéure of I—tmtemn, Pines, are! matter: (13). I In e typical prmtiee, e 1-1. time-necked mum-bottom flask waved with a me4maé stirs-3e, runes: canimer, drape-hag W, are» flex-master, m flamed with 9:3 a. (3.313? mole) of Edam-(Judgeme- 1,345.51. mi: in: heated. to 73" en the atma bath and 133; z. (0.39:: male} of phoepherms tribmsfisle me new imp-niece to the stirrer: alcohol at t rate affluent to min-L111: the meetim tmgmetere between (3-750. After the “Citizen m newbie, the me; ”e we allowed ta beef: on the Item: bath wrendght. The cooled reaction Rdfiim‘c m the: palm into 230 m1. of ice water. The aqueous gelatin m utmated with three ISO-ed... pox-um of other. The mum ethereal extract: were met-«ed with tree 1255a. . portion. of 10}: potassium manta solution followed by 11120 2:13-1:11. portion! of SW. After 611131.113 war 3113171311011! calcium chloride, 12-10 Other 1-: “ripped. W. flatmat- -011 of the residue 33131119111155 :. (73?) of zdwl-lfi-t’zmwmgxma, 11.1). 92°“ 12 um, 11;" “6” 1.21)? J. (-3) Immrrflmlopmaam (3) /" .323 .1?" 1'. \C.‘ .3 A 14.. £11ch :wnfi-Imtww £18.31 mapped with t reflux W, WW #Mar, am 11min; firm]. was elm—gm with 80 ml. of 8135‘; ethyl alcohol and 30 g. of zinc Gut. 51119 “$133523 mm at bmgxt m raflux 12191 13111111 111. a. (0.1133 min) at 1.3-6.1me- mprcpr; 113mg ma meat time.” crver a parted of 13/11 hour. After the 1123111131011 an: complete, GWR'T‘JIgg and 2-an were comm far _ 5.5 11111119. 12:11 11" gpazam was than £111.81! far xii-181133311011 and nap-ma. mhnpropano ml distilled dira. 11.7 £191: the mum mixture. 1101113151111 1.1m throug‘ u 1'" dam 51113- 1101109 packod column 3311113011 12.]. g. (333:) of imazmpylcytlapmgnm,h .p. 53 .3€§9.1°, 11316538. Baa Figure 1 far 1.2113 hazarm 331901213; W tin of £80m, % 103311333133 A 100-111. mam-1mm 9.4311 01511;:me with a reflux comm in: W with 25 z. (0.3 mole) of lawnmiaycmpmpam,13.5 g. (0.1 male) or aim-.71 «We, 23: :11. a: carbon Manama, an: 0.1 g. of 11 OH gonna: nun nuMGOHwbm: m oonmaonaodvhuahaouaomuu Mo 518QO cmnmuMCH m p a .H muswwh HA 4‘ _ fl a _ a—qm UN lo: OOH uo 139111181121; quag ad bmnoyl peroxide. The cozéainad reactamto ware rammed for five hours and $131 fractionated through a 7-9111?» glans malice pacimci comm. “tar ming the new inopmpylcyulcpmpma ('19 g.) and carbon tetrau fluoride, the mm as éistillod 2‘31 13313.13. mm was chtainad 55.1; g. at u nun-m boiling at 1“ «63° at. 5-5 m. The 1mm; tor 012119131116 m min by the mad of 8111109er (:3). calculated :E‘ar sprang: 61, 29.835: 29.53; 7210 infrared upset-ma (Ham 2) of this mammal 1:111th bani: for t W ring but not. for olefin. WI 1:: much mpmrpylcyclnpmgam m Wm photo- ohmn: with and wittmt carbon tetrachloride u a solvent yielded W Ml“. War, the new: war. very low. szoWodW-botwmmmppoduthnm mm,mmm,wamppmm1mwgadum 13. (0.0312 3.1m)ormmea1mtnmmgamd20m.ormvdmum. flmwflwmmmWZfl.damluumofSpor flucblorimtad Wigwam in 5:11. at other. Osmium-Mag msuwmmmmhmmnarthummmm WWWattnto mfficimttomintainn 3011110321111. mew madammomlm, momnumatmwdmmmm N-Iflrtormadditiomlmmu. . .3. ql 4.2 ma NH j- _..i.i-----_ 3-14- o919810.98anocandmaohaoao.nolm Mo 55190me 61.3.55” .m macaw.» 98.8 as :fl npmcoambmr .3 0H m m N. c: -1 S The W m tam cooled in an ice bath lad 25 m1. of mm m and: added to the curred ”1111.101: of Grimm reactant... The aqueous and arm liar!“ m separated. The organ“ hyar 1:10 arm-1 aver W ngmo‘m “Irate mi 1.31% (31.81.111.611. 1mm- mama}. of the “In: than an obtainad 3 g. (78;?) of immpylcyclopmmna, idmtifiad by it. physio-.1 mm cad. £11m} apoct‘mn. $1.110 ' 3.. cf (313: 6231th f 190M116 lap 1703113119 Om ml. at the chute command an 3:1th into 100 ml. of 80‘; mm mm (1:: mm) mintainad .1 23 13 0.2“ in . tam-matted bath. Pan-Loam 5 ml. 111qu me mad, mad the wlvolyail wmwummmymmtmmmzommtuecom “In“ athyi dermal. Each ample m 111m titrated 1111;310:111 delay with 0.62051 1 when: potassium max-oxide. 1mm :63 m “as: u 11. WW. W17 mimu indium an 25.0 ml. of hue m m to tau-.1. m the hydrocmario acid obtaim’oln from a 5 :1. Mat of €110 caution. Tim at. m5, )1, in mud mmmm tomdmriMordarnto much. I; u 2.303/t In: If" t '- um (mos-ado) tom. othuneomtoumumot the mantle acid obtainable in a S 21. aliquot. x a mi. of use mum to £11m!» the Emirachloxic tam present. at time t. (w) 1- mum: to the wt or wanton-5. chloride C‘v tins ‘0 1'31 11211311 1:. 83313: x 11713 0903” 2.517 01.: ié‘i‘ §1§§1 1:31: 0:231; $.87 The inasms‘flmy of 11‘, 83mg with the hufictteé dammrd trend of it. who w.- detmtod wroughmt an Want in which the 10113111331: .0 follow-d for 7500 moms. At the and or 1211- than, the min (5 n1. amt) ”wired only 0.135 :1. or bus to:- mutilation. 11m. mmmmmpmdum1mnw 1:de nu cam-m. um 35 g. (0.3 m1.) of 1mm, 13.; g. (0.1 min) or “mm. chloride, and 0.1 13.0: Manny). peroxide. Tho resulting cola- flm II roflnxw for 2.5 11mm». Wimfim 121mg: a. 15-inch :1”! 21.112. puma calm-m 1.3 mm mm: 20 g. a: 190mm, 13.1). 15.3? 11 27 an... of? 1.31.132, and 12.1 g. o: mm name, b.p. 175" It 18 m... It? 1.1.23.1. rho 11mm 73133: (20) for dimflmnmpmtylmrbimd chloride m 5.9. 1124. at 15 m... “12121 1.21283. 1 “13311013160 us 8311'. (fined on “1M1 01110231110). mmu in Wish carbon tetrachloride in. W n a 001va Wed taunts which we mtially the name I. thou "perm in those mm mm carbon tetrachloride m not and. Ems-11:21:: in ”If-1.11271 W‘flma ms (3111013121111: pho‘amtmmcam filth and 1131121310111. cm 1111123331125 as a 06113631; 533.113.2941 similar mu 0 To £129 Origami mamt 9:193:11er from 211.51 3. (9.183 mola) a! 1800 pawl We and 11.5 a. (0.19? 1101110! stamina twinge in 1 five:- Wed m1. flaw-hacked rmE-battcmaé flask equipped 131th I Emma; curl-u, cit-upping 11mm]. and ram comm, acetone (9 3., 0.183 .01..) m added dropwlso at a ram mfficimt to maintain a mum reflux. AM the militia: a! Imam m mlsw, tho motion W ”mm-tuttrowtxvammmmmhm. momma“ mmuonvmlm thenponru mwmu. of too-comm sulfuric acid. mumgmmmmmmm. fiatqum um- Mmm‘fitb M 5041. Minot“. $1100de Mme-muddadwmmmm mammal. other an m chipped 213532.111: mama. mwwmml "mutual-1. mmmummmm. ”Manama smarmaaaotcold commend Wtwda mid (hand on the theoretical yield a! M11101) . This :11:th m “QWMthodndormm. mammal-a mm. memmnddedtothe mmnml. and the mead-arc of $2.12.}:ng mammal}: ms moat-«d chafing the: 3921. Mar. Cam-o tug-ah: the 1m law: was mmted. The um layer fmm tho procxing camaraion ma em: ova:- m’ml mmim taunts. E‘iztmation mam-ah a six-1m): V1 323mm calm 31916206 1%.? a. 531;?) c: ciimt’ivliaozaroyylonrbiwl cE'aloricie , b.p. Ems-5:8" a. 1324 m, n§° 1.24170. f e «at "av'mlfimiem A min-um at 26 g. (0.3 mm) o: zficdimmfimmne, 13.5 g. (0.1 solo) at almryl chloride, and 0.1 a. of My). We no mmm tor an hours. Distillation of the resulting 2:1th ymmad 13 g. or agmnwlmm and 5.3 g. (3%) or dmmimpmp'flcm‘bim chlorida, b.p. vac-115°. n30 1.343.704.3172. M4 Iimlaprozwyhafimu m praned from diagnlopx'owl 1: atom (3.2) by the mung 32112133 Miriam or t3» Rolffczttistmr remains: (22) . In ; typical preparation, at 2-1. tin-necked mmd-fiotmwfl £1231: Maya: with a reflux cwmdmer and thammm m flax-grad with 65 g. (0.33 mm) of ammgyl kewna, 97.5 x. (1.73.; misc) of gamma: MWQ, 5m v.1 . of $131-$329 glycol, and 6!} :51. of 852': Izattmim ImEmta ., Tho metim mixture was refined for one hour . Tue upmmtuo u than titted far distfllnuan and I Mm a! mtcr am dicyclormm m an distilled mm“ mm m pot mum reached 175° c. 18 The appamms $32.3 £32.11: kwungod for :33“? z and 1:313 521714;: on ma 3'."er Maw We: rm‘lmc far 2.3? hours... .1:-3:21pm m then ms for dis. mum, and (sauna. boiling up ta 113° m collaatvaé. All (3th- htan we cmizimi, uprated from «1153:, and dried over 311‘“ arms mafia; sulfats. fiisfiillation yielfiaafi 33.3 a. W“) of 61m1W1- . A- .4 [syn 2: k 20 "$1333, bop. {Jjodfl‘ldj . nu.“1 1¢:,::..4’ ”13 103213. Civzlcrirstion pf Pierrlcfmrywfieng The apparatu- mum of I. EGO-ml. two-necked mai-tmttwad M equipped with n (117 133 comicmar Ind, n at Won who for the aé'kzdsaicn of chlafin-a. The flask ml imam! to ”Mmmly 1/3 its depth in 3 bath of rim-13: m2“! lemma alcohol, and than cowletely unpaved with almmwa tail mm for I mu mow tmgh which the wear: ma izmdiatmi. 01W 1e! mbctod tron the cylixxler $2.!szng 3 flat m into than mm: (m the aspen-elm tube). IrmEution in: umlwxai b; m1: cf :1 Ema mam: we may m. In a @1021). emor'mfiion, 1’11 3. (1.75 miles) of éicyclopmm'b mum and 1-30 m1. of carbon tetrachloride were placed in the award- “on mm. mm ”mum m imc‘mmd and chlorine m pass-ad into at u u m» of 0.55 1./z:‘.mf.o for 70 mm. M m of man tetmchloflde mm mm flicycbgroml- ”flan-WWW, therorminod «'52; a. «mum. mm mm trough I 154mb hence peaked calm-m fish-3d 5:2 3. or u chlorinated product, b.p. 634$ 11‘. 1:: m. a? Limo. . _¢ . ~ ‘ _ .. ‘ V: .._._ . . " ..-_.. v , "he immr-x’ mast: (Sigma 3) a: 1.1.3 “1.2.1.4 z...- shmg o...1.‘”‘1n ham}, and blah attribufiahla ta t‘m c‘rflapmmne I." ".a' . V ‘ IQ, _. A up aw i at. W Anal. idem. 3r .7211i..l: C, 5-54.)?! ii. 33-h?) Cl. 27.20 fauna C. ‘32}.ng 3’ 3.51351, 2.3.3.3 1. 53:34:21. trauma. wfimbottwm flaw: Wippad with a Eanh—bm'g mum, reflux comm”, am? chm,»fi.::;: Emmi ma chargad with 0.39.2.2, 3. (0.3305 mole) of mgwaim: tanning. To this ms added a 5' ml. portion a: 3 solution or 2:. g. of the cEMmmn pmhct or dicyclspz‘opymmm m 23 m. c: aficar. mu heating 2.211%.th the reacticm cm hie}: tho mining solution no 3136.643 (Emma at I. rate mi'ficimt to min" 133.3 I. ammo mam. Amaz- tam adziitifln m madam, reflux m con. timmfl for eight hours. At the and of {all time}, mtially fill the mmsimu had (Imppaamd. the running Grim ream ma mmw by cautious mum a! 20 m1. of inter rfillmmd by 25) 2:1. of ice-c.9101 1‘33 mmLfia acid. The am: and. organic hmrs we gamma am? the: 033mm portion .3 dried over:- wxydrm 38.316.233.233 wifit-a . After the mama]. a: t:- :9 ‘ her, iatillatmn 3131:3136. 2.53 1:. of a E'mmoarban, bug. lira-111°, :4 11:" 1.3.333. See Figm 3:. far tam 11$me {rpm-mm, . u an a w. cal-C'd 1.31. {3104112 'u, 330:...) I}, 11.14? W ‘ #‘ * , 3;: Wm arkad withanmw mdmbyacmmmm, 01th:: 8pm: 23W mu m ”bar, Mchigan, or time. Lab” 81:03:10, mm. 2O .AlmcopSQOAoacolqlahgoguoaohula no Suppoamm UmpdhwcH machoflg ca npucmam>da .m mu fiJ Shah m m M. w m ._4 _ _ fl _ _ P # 0: .0w OOH uotsstmsuedm queo Jag 21 a ma NH Ha OH macpoflz ca gamumam>ma m _ w A .vacmpsnamhopmoaugola mo Suppommm vmgmpmzH n _ m. — .1 mpsmwm Ow % m a: 3‘}: 2 mafiafi‘h 0’ Ch" .91“ E‘J‘fq of § “gage?“ Wt“ .- Ilfi'” 1;. A 500ml. Emlmm—eyoa' flan—‘5 eqdppo... with a Iflrfiberg atirmr anti Wad by an ice: bath ma czmgetl in 3.0 a. (3.6353 mule) cf the WW fexfmw'bm, £30 ml. acetone, 5'3 ml. water, am: 7.3 g. of mm mmta. The cooled metion mixture ms atirmd vigor- ouh for a. wind of 60 m. “am potassium pmmngamta ma um W by {.119 mm 01’ ”dim-a hWita. The mmem W m rum and Med with hm EEO-ml. portions of boiling “W. Th. mam m (211va of! an the steam bath. The ramming ml 061nm m «We: with We lucid, m then extract-ed 1w: I13 200ml. partisan of athar. The cosh-flied afiwrml 02:12ch We dried over £13me whims chlorizie, arm match the tamer m mad W. than min-ad 7 g. at an acidic momma. mm. 13th:: of thin residue a vac-1:0 timfiz 0. mil Gavan-plate 001mm 31.1606 2.8 a. or cyclopmmrbozvnc acid, identified fimgh its infmmd W and pinata]. comm. The musician from distillation ‘8 mm t9 1:: 11min, filtamci «3.19 hot, am man cooled in a bath a: W and W Mimi. Tim solid mica. mm In: re- Wmmnminw film consctadonamtm. Than ‘0 W 2.3 c. a: Mammmnia mid, mp. 35-39“. Ito infrared W at identical with tint of 311 «mama £5919. 23 B. 191'th and Docemosition of Certain 111mm Acyl Perondu m ' gm of the am min Acids WW and W114: acids were prapared wording to W (23,214). Cyclohmneoarbmlio acid ma W m Proton» Robert :4. am. Cyu10pentamcax‘bozqno acid “WWWmWh-mmlammwbfido (091mm: arm Chennai 00., 0mm, South Carolin) and cyclo- hcphnom (Column) respectively, wourding to the W decoribad in duh-.11 hem. mimetic ma mlnpmmouo acid- s». Wed from mum-owl chloride and cyclopmtyl chloride, respectively, n ducribod blow. mm «id at available than the organic muons my 11> mmmobyn. 8. Wommlrmt-Eim synthe- mnummmrbmmm. Thilprocomxroilnottpocifluny doom-Shad in tho 11mm, but 1: mm to other. which have: been W (25’). Cyclnhmcetio acid an we obtained mu harm Hm. I Amy-ml. mummmmmmdumnmg m, mm mm, sad drawing hm]. in ohm-god with 5.7 g. (0.331; 3. mm) or am turning. and 100 ml. or dry ethyl m. 25.; To flis m was 3,. I 23 5;. (C335: mils) portion of cyclera-strl 6mm. Gentle basting wtmtmi t2 :9 met an after which t2- :9 rest of 12:9 amicpzmtyl CI" 4.333.: 9 ms ails-l at a rate u’ficiamt to maintain a castle raflzm. I... a“: the an: itlan ms consists, the reaction wire was gnawed to stir for an mic’itiaml 1.5 hows. T229 eyelapsmtyl- MW cffiwiia 301:1: 2.9:: ms than pow-9. onto 100 5:. of cmsim“: c; 7 ice. The reaction sir-.mm ms allamd to m up until all £3.29 (L7 199 had éimppsared, at which um «Incl-mt. lea-com 1:3 suLMis acid was min-.2962: to miss the solution was: to cram m: . Tim organic and tag-3.9mm Eva‘s m9 amass! and has aqmas ]:mr ms extracted with firm 130-131. portions of ether. ms sum-99.1 sebum ms comm-ad and dried over magnh‘sus sale as: c :19“ ’9. arm rerxwal cf the sinker on ’19 stanza bath, distinatlsn or the rowing 37192591 20 3. (7‘7?!) 0: cychpmtanscarbawlis acid, b.p. 32-133° at 600 m. 11:3 1.33%. (Litmmm value» 79.9. 213° at 7.10 am, his 1.1531: (2 ) ) A soc-a1. tiara-necked macaw ma: equipped with a rum-mm m, droppim mm, and seats: comisnssr ms emcee? with 3.255 g. (0.033 303.9) of 7! 2:13:11?! 01mm“: I‘m-'dx'iefio and: 110 ml. of dry etivl 91:31:”: . 1‘s this us W 25 a. (0.223 3:16) or cycloheptarms (Aldrich (mammal W, W99, {31min} W with stirring at a rats mi‘ficiant to abstain a gentle: militia. Mm:- wit. 9199 ms 99991999, tF-gs nizrtmm N 93.10999 ‘99 stir on 5691919191 two hours. The am was man cooled in an 199 bath and myth-91mm by 12:9 slow 9513191011 9!? 9119.131: ics-oold 103‘; 99111919 acid to mic-9 it acid to conga rec: . '1‘319 99:99:19 and We layers m £11.99 99-59mm} 92x3 the: '9qu 99191199 1499 mm nth tub 100-191. patient! of ether. 1319 99213111in 9mm}. mm m dried over magma 13099991199 mrbomte .. '1': :9 991:9? me med 1:: V9939 and aistillaiion 3191:1536: 23 g. (337?) of cyclohaptmwl, hp. 133.1539. n3; 1.97.23. (lit-swam value hp. 133.153i:°, 9:3 1.9753 (27).) (b) szloheptorl Braids: Cycloimtyl braids as prepared from 15:19 mine]. and phospims 9: «:9. mm: :0 :3... mm o:- w <23» m 29 a. (0.113 9919) of mlahapml and 17.1 g. (0.0’32 mole) of piwspzms W9,_mm in: 99mm 23 g. (Gigi) or 9579le tax-amass, 3,1,, 93,0 .9 15 m" n? 1.1933. (mm-mm value 13.1). 151.5 at no m... 9?? 1.1995 (23).) '0 (9) (23910219me Acid F “a *I / UL, MMWWA9 “19mm inamneramlsmtc . 110 ma (page 23). mm 2.75 9- (0.1.1257 c. ates) 91’ 2511319911519 9:92:14 92:1 2:) g. (£3.13. 1:313) of amine- heptyl bromide them was ob‘almci 7 .3 g. (14,") of cwlohafimrrmfixxtylio mm, b.'p. 121° at 10 99., 11: 1.1.7151. (1192:9999 value 13.13. 13,? at ,. so ..,,. 13) ms, nu lei-{J3 (29).) mammnanmcctic £91.. A (a) Cyc lopmpaneeflmol 1 '. .N v" n. L 1-1. timockod romfibottomd flask oqaippad with a high speed stirrer, dry ice swim, and. $8 inlet tube as chasm} with 8 3. (1.1.3 3. am) or lithim War, 50 g. (0.55 male) cwloprowl fluoride, and 2550 91. 91’ pm. wmlcpmmvllithixm as prepared from this ads:- tar. as described by Fart and 3mm (30), and the system we cooled in an ice bath. Cams W'mme 0:51:19 (217.5 g... 1.3 90199) as mtvanced intothis fixturshymsofthsmsinlatmoauingapm‘iod crane:- halt Imus. arm- ths addition us examine, the metion mixture m 3119999 to stir in the cold for an additional tw hours. Sufficient ice- sold 10% auntie midmthmaéamtoanksthooolntimacm to songs red, and the ormnie and aqueous 1959:. m 999911191. The aquecms lays: Ill ”mustard with ”(mun czmm and than mix-acted nth tub IOU-a1. portiml of ether. The wganic fractions m oozininad and dried m 311'me 3“ ‘31::me mmmto. fiatilhticm 3191:3211 32 g. (:34 of mbprmecfi’mol, b .p. 1320 at Eta-.waphaflc pressure, 113" 1.14732 ,\3 Q _, ‘ / 5:22;. $3169 for Baamm C, 69.76; :3. 12.9.. 444,, (’9) Cyclogwyanaaa «#9159th Cynlagmganeat‘anol m catalytimil‘q Gangtm-omtad to 93:91:). pmmtaldefirio 999:- a catalyst 91' W 9:99 911w:- rzmanrrz an mice as dGSMEfif‘! b” Caviar an: Efmtgson (31). 73:9 ammtas comirtvsd of a cot-791' tube 1 flatm- long: and 1 m. wide, {5.9 9399?: as. 9131:3999? tm mm}. natal 23A!) tats-.19 joints at 13:9 W 93121 bettm. T99 tub-9 m9 1119:7191 with 2-39. 2": mctm wire £91- hmting am! inmlntad with 99999199. A mm- tfimmmh m1). m9 placafi in the niafdla of €29 tibe in men s. ration that 0:9 tmtna at tin 992w of we cola-'91 991116.99 cm. A caramel-alum]. ammo attachad to a Lease and. 219912ng model 1315 potentimatfr has aging-ed to thiamine t? :9 twm‘atm‘s. In mum, a ETC-«1. t’mammtmd mum-batman: flask was attached to the) bottom 91" tm cuppa? tuba (mick «as previously pae§:9d with catalyst) by mans of {£99 stall fitting: and 1 0.1151919 skater 19.! from the tsp of tha W tube to an 9:319th comma-r, which no in m attachai to a weaker malaise; a second 90119931999. Th9 waiving flask ms umally «12919:! in an 199 bath. The cor-par tuba m maz-mtad to 333°. 332:9 911 mm was heated by means of a hot plats to a mam 50-3500 above the boiling point 01‘ the alcohol to be clamrdromwd. air as intromced firm-3h tno inlet tips at a rats of 0.5 11139: per erts. mo alcohol was émppai into the Imam} £1393: umgh the droppmg farm}. at a rats 91' 93999999901: 5 91. per mm and the 919933919 was 9911th is £39 race'aivar. '9“. a. '4 In a tfl’ifiiifll pref ration , 133' g. C .6371? 31:13) 01? Clflfififi‘ymfiea u‘m‘ vb Wane). yielded 9 g. (is-:35) eye immumeehflddflmflc , b .p . 151'? 33-1332 , ea 2‘; c: ......m~ .- . ‘ .,0 n11 11,;53“2, Imp. O: mmflqt’mg1lv'l‘31‘m3m9, 11’; o 595':- u‘..- e, .r " a! - " ~ .I i A 4 i'J‘ , v, " F” . ! “418.“. £02.“ $1132.30“ : x!" :3. ...—3 3:, E I" to!" 13.1,; 2 ;'I .' I c” (c) Cyclopropanaecebia Acid [>£,E?,CED,ZI A 125G14- iodine M m 63mm with 6 g. (0.071 mole) of mlapro- WWO, 35 g. (0.132 mole) of silver oxide, and 2:? ml. of use. The main: m twat]; [topperml and academically make: at room mm for 12 hours, m which it In med from the shaker Ind heated at 60° for one how. 'i'ne silver and mining silver oxide m rum and ”W with seem}. portion! of ether. The aqueous. portion of tho filtrate m extracted with fear 11’ G-ml. portion- or emu. the m1 cautions were summed and dried aver awe/tirade calcium chloride. The other was Weed- En vamo leaving a. residue, finish upon distillation, flamed SA a. (7:???) of cyclopropeneaeetie acid, My. 900 It 15 m... lap. of pan-bmophmcyl derivative 53-83.:3". (Liter-start value hp. 90° at. 1:"? mm, mp. of gem-brmophsnacyl deriva- tive 53.5381; (32).) 2? «laden (a) Cyclomtylearbinol DCIIaQH Csmlspmtyhnmeeius chloride ms prefixed from 23' g. (0.233; mole) ‘- 4| - . - nee-acetic: {163:3 cyclopeazizyl chloride and E .7 g. (0.231; g. Item) mmesflnm undue. Fonflufieifie, gmemted by the depolpnerimticn of 11.7 a. (-3.130 mole) of parafamalfleflgmle in an oil bath at 233° 33) was 3:1tmducsd in a 31m: swam of nitrous: fldéeugflx a gas 5.31133 tabs. After the peremwe- tmte wee ccnplemzy dayz'kmeriemz , the nwction mbztum E18 allow: to let avemight. Sui‘f‘icirmt ice-deli} 121213 3mm: acid as teen added to sake the mlutian acid to conga red. The organic and aqzeous layers were separated. and the aqawae saunas ms was mmmted with sodium: unwise and untested with 190-21. of ether. The cerium organic {motions were dried over wad-ms potassium carbomta. normal of the Other 133 I. residue which, upon distillaum, yielded 133 g. (3;:-7;) cf mummamx, hp. 1-32“, :1? 1.15.36. (Literature value b.p. 155°, 11:0 1.3133 (3%).) (b) Cyclopmtylmrbimrl Bmzdde [PW/6133,32. Cyclogmtylee “Lo-Lmrl bro-11 do was pregamfl: from m1 .‘ mtylaar’omol and phosphorus MMB by a mti‘wd comletely amlogma to that. «gala-m: in the pregmretion of mishentyl buddy (page 25‘). 33 From 15 5' (9'15; ”313) ‘35 1330'333102‘11! tribromlda tiara was obtaizm 13. r“, 1 3 "4 a q 0 If. 21'; Q ”,1; g. (33);) cmfipmtylrfib... 9]. browns, b.p. LC at ..u m. nu 1.44:. A I. 25‘ 1 II 0" (Litmtm'a mlua ‘b.p. {if at ‘40 rm” m" 3...;39'1‘ (393-) H (o) Cyclbpmtnneacofic Acid ammuc mid m prepared by : method analog-man to flat and in tho taxation of cychpmtano anaemic acid (page 23). From tho Grim mamt formed from 10.1 x. (0.0?2 mla) of cyclopanty «- carbimrl broniéo and 1.51 c. (0.042 :. ttom) of mmasizm mm: than 2: as obtained 5 g. (”.33 or cyclapantanmcetio acic, b.p. 22".:30, 21.! 1mm. (utmtum value b.p. 2234223, 11:33 1.2520 (35).) I‘rmv'a‘icg 9;" tjt-a Ag; {3:13:31 '3 The acid $102149: mm prawns from tug corrozspmllng aegis b: either 0: two pmcmmms, wcfim with bmoyl chloride; or Mention with tindowl chlarLda. An min of each procedure is givcn below. ‘1 Crlorirfo [>ccu L loo-ml. rumi-bottmmd flag: eqxipped £31- distillaucen m abused with 22 g. (0.25" 12015) of qmlcwmmmaflwwlic acid and 7'?) g. (9.5 mile) of hamsoyl chlorida. Cyclrrympmmafimuyl chloride ma (313‘;in directly from the urban ani: upon radiatinatlon timra van obta‘mad 19.5 g. (732”), m». 113°~nz° (limrmm talus b.p. 11:2»11:o (27)). Chi-“Jada W A IUD-ml. raw-bottomed flask oqaipped with a reins: 60me In. wax-god with 10 g. (-0.038 min) of chlapmmecaraawnc acid and 10.1; 3. (0.092 mole) of $511va chlorfie. mm- the initial reaction had Wrist-2, tho Optimum Ia: heated gently on the steam bath for om hour. arm 12% distill-mum, mm m obtained 8.6 g. (73:21) or mlapmnmrbmvl fluoride, 13.1). 1323-1300. (Literature value: I». 15:: 3:9" (331).) I' L —.__ - ...-.... Prams. firm of 0?in Add. filrrir‘r‘s “‘- _. ‘*‘ w W Cyclapmpmmcetyl cflcrldr and mlcbmandcarbcmrl cit-la: 1:39 mm premred by the bermfl dale-ride procrfizm. leohwnnecaz‘owl chlaririo, qmlohrapmnacarbonyl c’nlmm , cyclsbutanmcatyl chloride, quepcntanao nasty]. chloride, and. @3103: awn-meaty). chloride mm pram and ‘b: the tI-ziomrl chlcrida math, 3. The yi-flda and boilmg points are 11315551 in Table 3 . rpmratim of $39 “335:"1 P-rr‘mdsfes The pare-nag. we prepared by tho action of scrim paroxido in mint mm 021 the ccmwm‘mg acid mm”. M apecific emmplas will be given. Q‘J ‘ .4 .p-o +_.— -a- A ‘4 o.--“i~--~ d: r-; - .. to.- M ".h' i-i fa: I. *tr‘.‘ {new M- "'4 (I no; v.0-A . ..g.-._ 1-. .- x ‘O -. .4‘: “ Sjm‘u I.“ --a-.‘-r~~FJ ‘ v‘pu'fiahhl U6 6-5-4 U 4‘. ~l-i‘ £351-.) "DJ-...JU 9*0- VJ “mas-JQ-wou- Edging-am xF-v-‘r9' ---9 ' mu - ='--'~~um an “mans ..., - u- - gnaw-agar ~4o-- ._—. -- unb- AC1»? C"; i_9“1<'6, R .5131 Y§.A-1_.;§ ”30’ 13-1! 1' Pei-:15; ‘1 («I V a D ’1’.” q as 7‘ ..l ‘J .H.” [>c 0..., 2.5;.- :- D433}. 73 90*)3 at 1.3 :m. Owa 71,; 110-122 at 15' m. __—_. A. M A“ 4...... A H __a_.__ ...—...... A ___ A ____‘ ‘7 ....— ..vv w.“ —— w w ‘1‘. ——' —' __ www e . ‘ ,_ _ 5, Emmy]. clenrisjo prod mare. All other! by be $311. e ~31 chloride procedure. IE: ‘3. A...“ J" M...- w ...! .3. Cpl-’38; 19V fw‘tjw \u'.~i “a, . ‘ :‘ 1+;U‘TUA‘D'V a ”W! —- " ' A 580ml. tame-1n 00. me: «hemmed then: «3.13.9993 $4112.21 9. mailbag miner, daemig Easel, mam: can-Jew, and a: new: late: in cinrged with 6.9 g. (0.033 @153)de pm and 1.3 ml. 0.. ethyl WWI. me perms-33:9 nu am to I flurry in the 6th” and there was the: ad... 0:. 1-3.5 g. (0.17? mole) of efiImeoml chloride were a pwied at 10 salutes. The readies me mended by the addith of 1-2 drops of wear . This came: the reaction to proceed at a m ..e 012.. *Eietmt to miles: the et‘mr. 1a ”am t2; 9 met .on welded and additive at a crap of latter are ledger caused an incrmee in the reacth temperature, the stirrer we steppe} and the pmvsdde-mlt were me armada-a3 we‘d-n Enter. Tim ether calamari was ten ”painted and dried over m‘ycroua 0&1:le emeride . Tile aqaeaus deletion at. thin point we basic to limes. dramatize of file e‘der in 3 «trees: of dry air left the «renames bis-ewlapropanal'onmi permdds an a waddle. The yield m 12.3 g. (33:3). The unique stability or this pmdds pardtfied it. to be recrystallized from pmtene (mp. 79.2-80.0”. Iodmwtrio analysis by ans enema. of 5min a a. (37) macaw: the recrystallised mterlal to be ever 923:! pure. ' ~1mw‘m’35“ E71 Freddie» u 9: C>w%-C-°~0~C-fir311ch of cm W. Tho mltmg aohrtian of Wimapmvacatic mid was mad. flfim’a cleanly in tho W reaction. (19) Cyclomwl Wfiwhts Do-M Cyclnyrom‘l WWhm in! Wad by the Bum:- mm motion of MJ‘CIDM’I Latex» with Wmmccuo acid. In a mum Wm‘aim, a 1%. tweaked row-botwmd “Wuthcm;Wgrm,mmm.mrm \LV ...} comtsmser was merged wfih 11.2 g. (1 mole) of dined-1m: lmirogw phea- phete, 22 g. (0.2 We) (:5? diefilapmpyl Ezetaee, amt 2:30 2:31. 0!: mafia)!» chi-odds. me ufilecmmm: 1.7 *- e 8.81:! 3:: than prefimsly described we need to t3 19 wil-eflnefi amt-y arm 5 mice cf 2;! mint-ea. The meflwlene 42211.net: 3 mixed elm-mg tide elitism 1.“? the muse: ms execute, the reaction mixture we gmfly reamed for one hour. The colitis were then filtered ans: maimed with 130 ml. of metrylem cifim'iée, are: the enema»: were collectmi. he commend 1‘11th m mailed with 150 m. of 15:5 Bedlam carbonate renewed by 100 m1. of new, end then Carlee ever gimme mmeeiun “Rate. :1er rewving the mwlme cilanfie by Cieflmtjm, them: mined a residue widen, m mum W% yield-ed a. We a: ester and. mam ketme, up. as?“ at 1:? m. From the relative intensi- ties of the eater and hem 12mm in the miemc". mum, it me :3an tint the enema contained 35%;" ester and LC 4",}: kahuna. flint-e mkprepyl Webemhte and flicyelopmwl ke’wne boil at ”5me the me tamereture, it me not possible to aapamte thee: hy mmm. Repeated exempts to who the remain by nifmeompfiy an activator} mm , 1min; pentam u the ehnmt were mceaeeful. “rest ammimnta to (Beam-.113 the 1W‘et1y1ty of Girmfid' s me an“ '1' em: ? (3;?) tmemfm flawlezmgyl mum rammed, in each was, in mtially mute recovery of the 11m! used starting mm. It as WW Waxed that. dicycloprepyfl. kctane meted mam-1y with byrirmwlamne mmchloride . In 3 typical mum, q a 3‘3 :11. 3222133113232 “12.3: may “1-3; I1...) a. reflux condonezr me 6132* 53:3. with 9 g. of 1123 est? :3" 2:313... abrtmw, :3 5. cf weir 1- trains: Igniroclfleri-iie, 13" :21. of Wei; 1:11: , 322221: 221. 01' abmlute etiyl 33.232231. me mature Wme m 323.4132: .2 :32: 1.5 .3123 arts-2‘3. 2.2.1321 t1; 3 11.131: 1:23 and. elect-.01 w re tween”. 311:... 2:. . Careful «3133232211311 of the mafia, 313112321 5- g . 91‘ cyclopmpyl cynbprozmewrbaxyhta , . n .v ' . _. ._ p . - O --' _ A mp. 1:..3° at 31222333333 measure, :32 at 1.; 1-33., 51.1.5?” ..3, 02:90:21.1- cation equr'elmt (1.0) 12?, 3313313131 12"}. e F. ... g, f y“ f 9 s kWh-.3 C. £31.)“, 15’ 3.3.53? . ”3.52:3" Mr" 333"“ at? 550-111. 232.413.3732: {he}: m a: meg-x2 312:: 23 ml. of pyri 2.1:. g. (0.83.3 3.33.3) cf cycloprmm111, 3m 1.. g. (3.033 22.213) of cycloprcyanaeee‘wi 333233130. 'l'fze sirene we allowed to stem: at roan Mama” for two hours 5.1 ”we 31.1 :2" 2. ‘ was diluted with 5:0 :41. of owner. The 0222233331 5032211021 ma "332.322 in tam with tan 1"” ‘-. 1. {23311333 of utter, a 23-321. portion of 521 WWW mid, n 25-111. wrflm of 135': 33:. 13:3 Garb: 3333, an; £123.12“? 3:}. 312.. fin-:21. portion of mtm'. after 621/ng over 2315233233 92113323, 1 3 e‘ulver we rem: ed :3 2:32:33 513111- hum t‘. mm 3412312321.}. 3. (72‘1" 61' cyclaprowloarbnvl cyclopmmne- acetate b.p. :23 '2.” at 2 mm, ni’ 1.11.79. us ‘0 ’ n Eat-:31. {3313'}. £92..” “'6 t?1¢03' C, 70-15;} R. 8.075 Tamil: C,-.- ’39.33 :1, 8.393 Cycle: med «3 e30 mama-m “‘ 21:12:13 ms pm! in the name names: I. cgmlopmpylcewim‘l cycbpmmamce‘mte. m S a. (0.63.2: male) of mmlnhmnomzhomd aifiori-fza and 3.33 g. (0.03;: mole) of cyclehwml were we 6131312233: 5.23 g. (733.525) of ageloherzfi. mlohmmmam‘bmtglate, mp. 132-231.: at 13 31., 3:5 2.1. 3.... (L meg-a values 3.3:. 132- 33" fit 10 ”'30. 11:01.2; ‘20 ( Hl) ) C'M- "of; par flnmnw‘r‘f, math-Wm CyaleWiwl cycles-23.233332233123213 19.: prepared in the was m u eyeloprowlcarbkwl cycle-pm acetate. Fm 5.15 g. (0.035 ml.) at mhhmcetyl chloride and 3.53 so (0.835 mole) of eye-1o» 3333333231391 two as. obtained 5.7 g. (733?) or meme-2w). Wants. b.p. rent-5° at 2.3 3;:-... 3,35 1.1731. (Lemme "Jam, hp. 11332-11250 at 1:} :13. , a? 1.335??? (132) Q) Ph-emrl enmate me pregame by 1:33 Sci-Lettm-flaunmm procwara described by rim-331301303 (:2) . ffig‘fiw ; “my! Paws Pyr.‘ ”a ‘a «“3 1’3} 5*. 5 AD; .yfiTxf,£.("yfi 51‘ "Yr MN" mil 4‘...“- “an" " wwfifi:w wmiz— a?” \n‘. Tim cimitipn mass). omwiatoxfl or a 23%. maxi-bottom £3391: to the top of which an attached s mauled-on swam cam’mwar. t can twat babe, m'-$mimg to the bottom or the flash- , ma seal-mi into the: tap at cm 31.. a of tin vase-:31, and a; cola-fawn" gram-ems W was affixed. in 31"....‘Lar pofitian on the otizar. An eight m. glans Wm balding a timy 6"“?“0011. and wants, was atmciaad to tho top of the confinmmr. I 1me ma afizrdtted L1mu$ the 5m inlet me; it was torii‘iaci by magma 1t timz'fin a train consisting of em 250cm]... martian: of fieaer's ”lumen (:53). ms» ml. or 1m accents, 330 :01. or mmtmtad writ: acid, and firmly I timing tom fillad with 9mm: oalcim mastitis. The «it gases from tim‘ mutation was-.31 m snow to pass through I train Wind in seminal as rm: 3 30;: solution a! mailing in mm Weiflsrlfie, two cold trap: mm in airy icon- iaozmpyl mam]. baths, 3 tar-m3. new» containing saw-1m, mthm' pmtootiva mun-mm U-vtuba , e. um filled with anhydrmo, a new trap mhhhwi at dry 129499me Alcohol tmmtums, and I. «claim clmricia drying tube. In mm oases vim-em the «mm-mm ‘0 Wing used for kinetic stamina, tits emanation train tar mt m W on}: of an «wit-e U-Wbs am! an m‘mizma am. In mZar to We mm during the kinotics emu, the aim-ages: not: time}: mowmmmnmwwmummmomm directim thraugh the top of the: comment- tr; mam o! the time-any rmv: . £113;th me time famed cut of the 53.5 mm. me into a receiver. me reaction weasel, in all cases, we ens-3mm in 3 mm oil bath. Boating ms accomliflmd by a imfie-bhiie hmter mi someone: by a. wiiwtimty mm"; filmmcmtor commuted rim-‘13; a mes-r- Sax-fees almfimnio relay. me gamma in mom animation-11w in Figaro 5 . of Pmfiurte n-“w Junta-n. as Pia-cam ma datmfimxi webmflioal‘q as dipimvlurea isolated. from the aniline temp. Csfiam (use-hide use also ciatcmflnod gramm- ally by measuring the increase in wigzt of the tux-ed Wits who. All other d-otemflmtiam were mayfiefiaed by the use at qaentitative W, airplayfing the base line tecimque (1,1.- . Int'aa mmmrmmaitmnecaemryta detmtm unique hand. for the coma in question. It we also 1160085817 to dates-mm due-thee them bands named to anbwt-mgum lav over the cancer tmtion mm. mmmteree. in times cases where the detenmticn of peroxide. me being 3351*!on , and the Wise m not of 10055 MW; muons mm on ioflmatric analysis m mm in the éetemimtim or the await a! We in : 31m maple. mm mm the finances: to Beam-'0 law of tho variant cesa- ‘pumcfin mount-eras, mam-emu urn-e mats at three «Luring cw mum-(1n tin range to be m3m1)nm thm the cant-nae? ofgin tea Won log 10/:- m, mere 3 is a comment. t 1: cell with h2 .mmnflxosma anew mUOflsm> mo COHpHmoQEoomw exp 90% mew: mdpmswmmd .m mLSMflm mndp muopvmsc< sz was» opflpmomm mpflpompopm AAV xooomopm mmznm Amv mswpoaso esfioamo AQV mass mpflswomm Umpme Axv pmaaopm newcfiw vaoo on Uflow owssmasm ADV Qmpp @Hoo Adv xmmam soapflmanoomQ Amv mpmpmom emmq Amv mwpp mafiaficd AHV pmaqfi cmwospflz Amy COflpsaom m.pmmmwm A01 0.01313, 0.0190; 3.31, 6.90 [>44 0.3103 5.75 0 >003}! 0. 0 3.90 _ ‘ tuition of Biaqglmgan-ncetywxfl wwwom perm-51:0 m deem-$0000 by a. method “lag-0m nth first W in tha can 0: biomlnpmpmafoml veranda (page ). Tho pmxido «comma: vary rapicflq and mmmly (havilng wind 01’ six tum-l). The mi. 01' We 090W m corrected for marina by mm analysis. Th0 mount. 01' eater obtained an 0130 ”meted for the man’s of 011.01- mutant in the origiml perordée. mmuuuwamotmmu,mnmuubu7. 31 17...; 7 ~. --v . - “nu/"- P\ J. 9'1 5 """f' "‘ " "‘0 EALUCTS 511’in £111.11 ‘TQSITI'fl “ BIDUIWL"... I111 .....le 1’711111111 . 111' 71.; L‘1LAM'E '3‘31‘1 T73 131$”. "'11. 7 1”“. 31:1 Hwfi’fi ...-‘1‘ ‘ AAA ...;_ _4__._ L‘ALA“. - ‘ ....— fifi T v—v w-T w ———---—— WW‘wm .... ‘— 1... ... 1. _.__... 1.... .1. 1.... .... ——---—-— — --—LA --- --‘-‘~‘--fl-«w mam ww- w—W -—— _.' ww-~._———T_ _. v 101 . 41,5. 1. Flt-“M 1 0 0.83 O. 0.8;: ‘- w A“ *— ._n.__ A u 4-. ——A. _-___ .h'i __ _—l-_ ._ W “.7 f“... w a. V? ———v “w . .___,_1 W ‘— T E ' 1.03! P 213m .15 J3? . VG A A ‘43.; ‘1’ Ai— A m ‘11.,” “ ... . 7 . ; —'—... w." 1.. C w v [> mac-0.0406224 0.1715 5 5.2’ 9 Damn-Q 0.2922 5.7:; Dazscogz 0.53102 5.92 . __.__ _.._‘_ ‘— meme 8 330222013 33:: 0330303171232 (3' 33mm... 13:00:31. 3:30.111. 13 70° m 01:10:32 1:330:30303 303. 2.0 21:33 W 2201 ‘30: 2100.2! 300.2: 0001. 80 0.551 0.615 0.250 “11 0.151 0.1131 x w. L... W 2: L: : - A C": “kw—7351‘ : ”‘3: A“- w. w: _: 5:; W .. 1.51 1.57 no 0.225 to W. A “ ““1 :1?“ w :—— 3.“ 7 .. ...... A :— ;“‘” : : 3M rw I”: _ ‘C‘ M w __ ‘ "‘ “$7.. :34 ... __ ‘3‘ TI: w w I” mfilfim * 1-55 1.87 - 0.233 - C>cogx 0.2.077 5.91 T51?» 9 32:01:21.3 wwrwz‘: 3327". WWW: ' 2.2222 “221.9%”: 21' 70° 2220:. 3:222“... 22:10:20: ::2 7 22122.23 .4 .- figwi‘g 2 22:31 0:, 2:2 :2 2200322 01:1. m; w. :wh w LAW .... :3: ...._. A“ #‘A :_w A“... __ ‘12: 22:1. - m W m 1 1.32 1.77 0.925 0.30 m 0022.231 0.0375 11.21 “‘1‘ “And“ “ . a 1222317272223 222022 221.22.11.31'22322 232* 322's”; 222222321222. .22: 70 222 21223222 2.22.222222212221222 122322 72 2222223 Pm‘Oficii'G 2a “a a q momm Risa:- Cos Tubaafi R8113?!» 6x1. ‘0 105% 0.925 001590 0.0120 0.321 0.038 1 1.271 1.?25 0.0155 0.255 "' The Bear's Lav Constanta 4“ w 7‘“ ...“... Compound 3‘ (—--!--g. cm. . Afium)m W;w “‘2‘ __ :.:___ 3“ :1 fi:::. ‘2’. 2°. 6? :3 ‘ (:22; mt. this, refiner tan was $43th dimflwlcyclom-owlcaerI momma, m tor-mad, In: mmbly due to the 3%th Mr or were having hm Ii: print: and only am tm'tiary lmlroam, coupled fl‘dn the fact $21“ the tertiary position m wall wielded froze attack by the way). and: evolapmpyl gravy»: . me next 303.99.13.13 sign-r75. 3d 333 c misfit-333.39.33.39 mien ma 3.1mm: as a fiD’fWW' for admiration @631 the wmmisn tlzzt €13 mm! land to an Man-333.13% Limtloyrsyym’hiwl free .-a:1i....~". This apwcntl turned out to be t .0 case, al-Zt awn t a prociu at ma sham: t3 have uvlergm 33¢}..va raamngamzt. By 0: diction of 1.1.9 olefin obtain-3:1 in ties c510: n, it ms establimml ti at €213 pct. 33?. mt! l-cyclogmm'l-iz-c.’ zlomfmt-ana-l . >2?“ bu £flfiduua~q Tris remit ma malsgsua to ..E-at 033531331 by: starts, 3‘. a 13313.4 allylmrbizvl chloriée fro: t‘za cflarbmti-m or mtzqu'clam‘opam (13). In award with Reba-rm mumtim, it in pro‘mbla that this pmiuct 3.3339 frzm the mmxmmt or a (.13- momma-bum free radical. [>-c: —<]-- “Dzmgz-cnrczq It as particularly Mamet... *‘1‘ stint t. 9 mm...» W11- mrbimfl. maid-.1 am not maintain its Meat-1w. By many with t similar type carbon-1.13 ion, 1t 18 possible to tax-mute mm]. W9 cth which amid. 93311.1 333.3 to this mm. >24 >4 N m. II Ewen, it u appamnt {mm the m for product isolated that structure: (II) and. (III) 350.33 mm not part of a resonance 12be but, rather, mat ham berm (21.503032. intam-fiic.‘ as at the ting €222.22; rmctofi. with 1520 3.1033222. 'vwwr, 1.222223 mums a passlbility 21‘- 1.52 ...-.1:: not 122 casmfik.’ rule a at ti: 3 irtgmtanca of £222 magmas-00:15:19. t3: 212-320 in ct:- 2:“- 2.01.1002. .222, 81.2.22 $2.2 p300... -cct 2.1.22... 2" 2m 322.13 sub-tack! the mat nimble one c‘a..,r321210 £332 (25.0;m'lnpz‘cggrlvc’gzzma, ....3 mscfisla ...... £323 react 1012 (0. 2.1.02." J21; .1022) 222.23 82:“) wt to t7:a:*3—.0*:‘; ..3... 23.0 02:23-21. If this we tits me, than the p. inst cbmimd was .120 022-3 26.1212 2:22.323 be etc-33* . ...:‘2... Errtkenmre, 1.329 carnmtivaly 12:133. $121.27: 01' mofiuct 2-2.3.23. at vary 10:: 1.2.3.2323: 2:13:22. be t.‘ 2:: as an 2.2.13.2 t12:2 01' £20 22212.212'2 00.22 of: 532-: £130 of t; 0421.2;r‘2322" 332243221 miixl. It 672523.13 1:0 point-:3“. out t‘at {:70 3323252212.. 1.2022222“ r-2::-2::t 10 not 22!. all an usqml: mainly ostzbllfilzefi as u £2220 122.61.24.21. I‘wction, 02’. *3 :2: 1:2 tag prasm't 1:;-2:02:20 or in the 2:02“: of 22000320 (13 . 53.1202 13th 0.2.0310 19 pmfucad in q. 2.212.122!- 0:221:13; the c1~210r4mtiom and sin-20 it 18 1:220:32 that Cg-‘clopz‘am haogiwl 01110332.: 1021120 73 .7 ram .13 (1...), it is possible tint the 05322222221 product ms pmmced by a cub-3:20.212: ion rummagemmt. Such rmgcmnta are well known in tE-Iis system (1.3.52) . .2 § >092<1 + EC]. ---9- [>£'E<] 4» EC}... . 9 >30 -- >- .. cit. f. ‘ “-1 "a tv >spwo-l‘o “3" “I, . hula ”D‘AHM 1‘31 . 00w 13. 0mm (Emu-mu Romain; the 1.0002222303223100 0! Acyl 5" 312023.103 Sima a mjor portion of this $721003: 00313 with the 0000390013100 0! Alissa-110 0.10031 pmifias, it will 00 V833. to Mimi brinfly the amine 13.2mm on this meEnnis: of 00032 W239 éaommofitiona‘ . An 3071 0020:0310 my margin mammal deoanpoaitim via u how-- lytia fission 312an the: W135!!!“ 3010:3110 yields 0m 2000 rat-3.00.10, .0. 3 H-C-Wafl W 2160'. a, 20230: certain conditions, it my mlarm hetmlytio cleavage to 3101:! initial]: 1 pair of ions (:53). O O D 0 u H H . II _. HW-RW Ric-0 O RUG-0 It tn: 23:21:11; 00m absemi 22m. 03:0 tamer “taxation pwmm for rmtrieal mam 1313;103:3013; (1236031510823.th in ralativoly am- polu' '01ku such as carbon mncfiloriéa, 00mm, 25231300322103”, etc . fin.- 2:009 of (1.000710332121011 by howls-tic fission of an mygm-owgm but! in probably a common of the relatively low bond Mum mm a: 2m pal-31303:: bond. 23.: when o: the bond dissociation energies for 0.0er and bmzoyl warm” , £0:- «01.22010, have hm “muted 1:0 be 0m 27~35 1:11000102'100 per 003.0 (51:) . 0n the other hand, the 000302323: for acyl paramos to (Enema 1:0th is increased by a (300mm of 950mm“? in €220 021ml mine-ale. In mmipm, this 1m» 0:? (Escotmition my 22m {:33 entire {smut rm 0:32.3le diameiation 73 into me- 1mm , firmly: ion-gnu taxation, dam to t we polarisation of the mq'grzn-ocqrgm bond . 0 0 H H RflWflI W ace... 4' 31.3173. 0 0 H H a-c-o-c-«c-zt 4.”; .w v “=36 ‘) (mac, ) 33-0-0342! Mun-166m. "4:0 It 10' many cumin-doc? tram the above that torrent: or Mgh dielectric W mid favor WW3 cleavage of any: mad“. In Addition to the upontaneoua éaconpesitiom discussed than. an icyl puma. my unciargo an mucsd cimmticn caused. by m (65) or by adieu. (55). An magpie of then form: reaction 13 the thgon in: «W dacmaition of mathm'l-p'qimbmzoyl We. Wymfigfl. ...... c». ”Mfg ..LDJQ ...... NJQW. “WMWhmrpmmuthéelnmgootbmylmduhy in! Muhmlmt‘wl radical (66) o Rawhm‘lotw in W collation diluent-u to I mid-able dim into triphwlmoflvl radian. mmmmmumlmg (nthndryorm solution) a rapid reaction new! In room mm; 30 urban dimddo 18 mlvod and the mane“ m bmcia mica, Mtyl lambs, and tetra- phmylni‘unne. ma proposed mam-11m m d fallen: (1) (German. 0 (03:15de chsco. Means), o cargo” (2) (ccfichc' ‘ 03335303.“ 63.35303 “6335): (2.) came o manage.” (35%).0 Reaction (3) chm my not take place a mob, ainco no carbon tumble no dctcctm. Rather, reaction: (3) .116 (2;) my be mum. 6.3525(3930 . Ctr-‘35 . (33313); CO” CSIIBCC'H . (09:16)‘ C 7220 1mm step in the free radical momenta of neg-'1 pox-omits bu bun a uubjoct of m emanation. arm- thc mo radical. mm c: the 9mm hsd been tcccptcd, it In. postulated that. tho 11mm ”involved mm mpmroortw mmwu W band running in the {outta c! talc molecule! of carbon dioaddo m! m mmbon mecca. (57). Riflfl-gcfim 271* O 230. Fma, t!» appearance of timfiicant W of eaten: and acid mung tins (imam product: in them calm tam-c nuanced dccmmition‘ as W, corn or lease eerzcludcl this which. If. m Inter “mental (-53) that $326 initial Item yielded u moleculo of carbon ciimdéa, In acylcn radical in: c h' "rowrbon radical. There in: ccnsidm‘ola merit in cm: czphmticm in tact it mammal tar tbs mm of certain deccwcaiticn We“ u tell an Iowa rats 53h. Hon meant investimticns him indicatod t2)“ Ln my). pmx-ida upon W charm]. daccmccitim ymls initially two acylcxy mains/118. R 34-0-0346.” ZIJJC‘f— -H b productl Far «maple, lbs-man: (59) dwemoscd bansayl mime in carbon tetra- chloride; cmtainina an acct-cola:- qmtity or 1061210 and water. There ‘3 obtained from: this reaction 3 quntimtivc yield of bcmoic acid, thick In Mica to ban bean 1‘ch by man: of the following flaps. C figmg-O flaw 20 Jig-8.0. 001358-00 0 I‘m Cgfiatg-O-I In other aunts, aims the yield a: bcnmic Mid an «autumn, if. m concluded that the initial dccowositian step yielded two mu radical. thief: Lmfiataly ambit-nod with the vary active mung-Ir 103.130 to yield at ucyl W’icditc. This in mm m hyaclyzcd by tam cater to yield bcnwfc acid. In a control morimnt in the absence of iodine. no significant amount of benccic cci-zi ml pmlucod , the principal vacant: being ems-ohms and ha-Mflpmcttm . In a m 0: ch: ammunition of acute/1 mm (72;), it mm mm flat the pzbéucts cmld be machined only on we ”amino that 73 one dealt many, or at least to a. great extent with lactate radicals which dammit” u timy met. A more detailed minimise: li‘zich explain: the origin of all the decamceition product. obtained will be givm later in the dimension. Sam]. detained kinetic investigatime of the fro-e apical decmpoc nitiem c: ecyi parmdflco 2mm been carried out. In essentially all wees, the kinetic. could be exprceecd by the following equation: igl - he (1:) . k, (p) " (7:) (P) II mutation of perondcie Re gnaw tor epcctenm‘decowceiuen k1 Inumtormeedmeitim r. I are.” or the induced deemiticn motion mm,x,humnybmfctmdtourybmo.5m2. Iii: oterWhmiotmtmmmtotheprecedingmtim, ecyl peroxide Wait-ion. m of the rim order Man: it Wed ammummmm. mimmmumyimomnmmmmm mmmumeummuwmmuu. Itierelt mtiemmmumwmummuumu mmmmmummmummumo MM. Includedinmdilccmuinbethermlucbteimd intheceucfenen-bmoyltypepmddeincrdwupommaih {mammauamnmmmunuwpm Fin-11y,“ “thfltmimifimumetthemimemiledmcmm tandem to mm the origin of the various docmpoaition products chained should be a: who, and, timoforo, those till .130 be incluooc'z. 5min, in t My 01' tho doomzposition of albatitutod bonnoyl perm-Moe, rm avifionco that. tlmy denounces Wm of electrostatic roguleion com the m bmtfl grow: (38). @M@ W a... Q... In otoor mrcis, it me comiiorod that the molecule consisted of two dipoles 03-1th with ozone mom m max-est. each cow. Such a nation would emu e largo oloctrcoutio repuluon which would tend to force the rmlocolm wt. Taxis o-om apt prodictoo that electron- musing albltitum‘bl (689801331? time-o much were situated in the pars position) locum 11mm» the mic of decomposition 1mm ekdlarly pieced «lawman; group! should decrees. it. The mice aim in Table 11 illustmta tide point. me elootrmduithdraring oymo and chlorc mp9 doom-o the rate (with respoot to the wmomd peroxide} , tome the cloctron-rclouaing methyl and nothoxy’i gouge inormoo the rut-o. Tho effect, banner, in not a vary largo one. fine rate of oco-mwoeiiicn of homey-l mien vorioe mnwlnt with ' the what also in the docoapositim. This my, banner, be no in part to imomoioe in correcting for imiucod docswooition mich in highly Iolvent oopmiont. 5cm raga-romaine on“ date of thie W' n W in mm 12. ‘ T‘m u n nonwocmm (P W amen. manna IN DIME AT 50 C. 1s mm k; x 103 (mf‘) M” W 7.3 mv‘ W1 3.6-. up‘ W :14; would. 2 52 mp‘ dichlerc fl; Wu 1222 ”Micron 1.02 m n m to or man. mama mom :8 mucus ammo: (73) rap-um ’0. .1 m who. ) bun-Inn 50 1.93 I: 10". bee-let 60 3.28 x 10"” «um Amen-1o. to 5.55 x m"8 mu unvarie- on 7.5 x 10" m W60 80 m2 2: 10"” tom ca 3.25 1 19"” um 80 3.23 x m“I W so 3.23 x 10"“ W 80 ms at in"? W 80 6.36 x 10 6 W :50 2.25 x 10‘” mummmwumnbywmcm. it night ”on won? .4, tzora in 6. largo (givers). .y in the prunes obtained from tho m3 mion] dowz’gmoitinn of hwy]. pormzicia in difforont eolrml (73) . Thorn an arrow]. factors much cwtr‘ibuto to thie citation. in inner ’31} part of tho prorjzuote finally inola'tmd is prodnood by reaction of the from roam]: from the pomxido with the mlmt. also, most of tho doomqwsltiom have been porfomm". in wloé time of efifioiont concmtration u to allot: imucoo doom-open ition motions to become particularly immxt . Ynoroi‘om , proooots malt» ing from tho mhooi (3330*.4‘3'131411 c: the poroxifio by solront ratio-ale will of courts: be éii‘foront for Gifformt variants. Saran illustration omzxploa of Erin are zivon in Table 1.3. mxo 13 was? oars no: 117:3 "snowman or "2:3 I;- rm; 1}: moors gamma (73) 03131ch CO”? 611360333, O’Nefin'c anemia. 2 n n o 4.: ~ * a: cé‘fi’c§‘*5b9“11305“6(’b3 baa.e Carbon tattoohlorido 503,3."13515 CC 93,3281, C,Cl.,cg}t .171 pg Ewmono 903,.6..5CU, ,C 1.53:“ min mine-ts, m. 9881!], 3&158v’fi Uniizc.’ Mpnelni co (.3 A mommy @9941 m or so anyone poo-min damnation at Mo by 2251m- amfi waist (71;), who union} the damnation of bioc- dalu-pE-zwlvnlmvl poroxizlo in dilute carbon totmcfizlorido solution. It In magician: that. a (Knots solution or parsed-tie in n compamtivoly motive solvent such as carbon tomcfiioriaa caused the amount a! lament} (Eocoelposition to be Malig‘fible. mm Woof. Moi-.1 13 1mm in Table L's. Tlmy wore chin to accomzt for 973; of we cameo éimzizia and 837.593 of the piaml‘mtyl maps. It. would be noticed. that comm dioxide and 1-c3floro-i4mhawme m the mica- promote. mmm mm m3 Effifiifi’an “at: a? 13.9 :mrmrn w BISQEETLM- mzmwnzzz mm. 32.3: m @6333! TE??€A££&G’EIDE (71.) caflaczza-cztwmrcnaa 12.2 cool, 1.1 EEC]. 3.5 0,3 2.7 0333(6313).CO,I! 1.1 cagcrzgfiogcxghms 2.5 Canaan), 0.322,, 3.2 anagrams-e1 ca. (:01, 1.5 ”A u A ._ AA)— A‘. .....L ”...... M A_____ “ “ ...... , w fiv—W Ww—w—r www www ‘— “Tow—vw 81 In union to :2: Was the warm obtained , 12222212 am! 2:32.: prom the following madam: ‘ [6,34%(3: .12).;3x'1M Etc”..r(voea)‘bm.] [c.22.(c2,),coo.) ...... [c.2.(:2::,),-3 o co, 3333(33‘)" Q 001‘ m CQH¢(333)‘€1 . «3813 206:1, cum-II» 6.61, 2tc,2.(cn,)¢lmm m c.2,(o2,),c,2, ceoécriagv cone 3533 $90" 3389” Co? o(’ma)n ”(3,)‘8... cW’EE if“ 3)‘ . 039.1153 was ‘):'303. “EN 6538(3283 -::: a": 6:!5('\J 2‘) 33132333 c.22.(232,}.com.zz.czz,crz,mhc2, ~221,+c.:2 .. 22,) .2322,” c... (...,,,..:c 2,22% , c,,2,(c:2.)g322.22.321,¢rm¢-——> C 51433,) ,am,:* 43.2881, scanner-n. 661,023.31, or 28881302313” 03.300381,¢CI. (9“, ,300631,¢2,o ...... c;2.(22,),co:2:+coc1,o2621 It mm be nominally pointed. out flat in no one did to?” and 2321: .1101! for Wad donomtion in tho minnhtic Cohan dwiotaé above. M m W223 mm}, it to: £212. that this did not occur since the mutation or poms ma mu, and when tetrachloride is a midway motive solvent for free moimll (notice, for min, on largo quantity or warm mmnum cam}: obtained in one ‘ éWflm). In light of tho m invoatimtim pertaining to the product! mm from the dWi’h‘Lflh of beam—cry]. pm‘oozifie, T050132? and 2M (75‘) 3.23179 fonmflatad a rather mam]. 5212223231. 2222223111322: to 9222:2221 th‘?’ pmthata wammé . In the follmdng 2:222:22, P refers to €23 origiml pave-21:33, a is the 12mm radical, and SH and 82: are WWII and Mag-muted German, mspoctivaly. In (3.) Wm: cleavage PM £22. in (2) emulate: of w‘iical a. 0 3w 8. (far unsaturated or activity to 3012mm aromatic uolvmta) 30 § $23M 3" ‘5 IE} 22.. 0 333m 3' 9 (2.32. 0 CS. R. Q fiwfi- 4'. 5?}: H." 9 SEN S0 6 6322.531 0 CC" ”is (3) W amenities: 2% 9 PM a- 4» 226.22, 0 00. by R“ _ h (L) imaged (5.2002242021121221 8- 0 PM a. o 223 by So 5- 9 PM 2: 0 0.9.3 9 CO. . *3 (5) Watson R. o R. can-no pmducta af maturities! and ciiegaropox-tiwtion is Ho 6 s. ...... whats of minimum and diam-omfiicmtion .8 . o s u m W422: a! continuation on! disgzmportiomtim Although 1:22.312? and 22392621212 {madam 1:;-in scz-rxm for ma We, 52W 01' its mime amp: (with our without those we}: we head upon Wand Waitims) 22122: that» W505! by wrap and WELD, inflates mom-f1 aimiw batman the tan that it $53 153 €03,815fi‘fi'3 to be u Emu). Schema a? liable to all My]. p:-n~o:d££aa . .. Pregamtlan and Pwpertim of VMM £911 Pea-oxides All of the pang-idea usad in t? is twain, with the macaw-Jan of hwy}. maids 13621-2531 mu cammklly available, mm pm by the mum a: tan appmgzfléte acid chlomale with m pew-0321.233 in my). «ES-1w continuing a raw camps of mm. 9"“; ’10 Q R n-gan o mac, J—IL-e. 34%qu o HaC-l In them cases whats R in, the show equation In- cyclohagvl, melohaptyl, mbpmtyflmrbiJVl, and cyclohmm-fiwz, the pcroaddea m nous. m m an the 1mm, but limitiad at moan Wmtm. All of fins others, except WWai‘mvl parades, m clear oclarlm oils even 5% the Manama of the (“wager . Biacyfloyrmefoml Me an 5 mm mm mtwm amen melted at 79.83-60.55". It! mulling amw ans; mama). 33ml [ability tum: it to be purified by Wmmm from Wm barrow use. In $215 was of Encyclaizaauwazfim, bimycloIWOI-wl, and bimyclnpmpanmatfi pamxifiaa, ma 02‘1”]. lawman“ wra team: to man mil pox-£10m a: £1.23 :0sz 6m. ‘21-'11: m cmfiafi far in the mbswmt 3.:th catmmmfim and product amiyaaa. In Essa-a cam 1:12am no m could be deflected 1n the yum-mafia, and max-e the gamma; mu m not of 13333 “1%, u éa‘aamm by imbmtrio titrafilcn, 11'. 1119 {216991119 that 8993.]. 9.1119113" of 3911:9111. (31177.19?) "-. T119 9999111911 31.99.9913, 111 which €19 app. 1 1.91.9 parazzawa m tom, ma maximally 1121919 to 111m: at 1.2.19 9911911131911 01‘ the mum: 923911119 9919: 119339 13191191111119 not 9011mm. For both whi'wfiva 9:92-11:21. arse-.1339: and k1:19t.ic 99991911111111.1911: , ‘19 911151111 fireman eon-39111191219113 1mm corrected for metiua by 104111191119 911939999. 9519:, prom 9:33;” and kinetic damn-mafia: m porfanwé 9:1 0991199913 pmgmad 129191.199 of the marina 319119.11? :19; the basalts m 39mm in very 399:1 norm-11:1 . 13. Products of 1:91 23.160117130813103! of 50129 219931 ‘1'?" 9:951:193 1‘99 03.43.3930 at dizzy]. 96919111993 ware M191. “than my 119 my“. Med by the £91m gm]. fort-mks. f? I? A ‘ I J: (-122.13)“ CZE‘Q-G-Cr-Ll-Cfi (313.3% :1 .. 2-6 II (03 Ciifiilgqg-OihfiflIia-CH (821,)” n I 2-5' In all m, €99 91390211909191.0118 were performed in 11111196 951111911 mail-391610 0931111021. In the light of 1119 51:11.43: 9:? 29'2““ 9.21.1 ‘9’“- (page 80) , 1t- “ £911. that. this 91.399.113.199 111111.99 9399191091ch A check «wen-19:19:11; on 1.319 1.1919119: 111 than 11999911” of 10319 cmzfima'l 1.3118, and will be 61399959.: 111 the 93911911 911 13191199. For such of "19 above 199.917.1199, 199 111991.911: ware Wad in detail (Wimtimly £119 quan’bimti‘mly) 1111-911 n ma 2 anti 5. For ot'zm' when 91‘ n, 1219 1129:1111; 9:?! 171-9 {1111311219 119.: 9911133119295, 911:1 9’19 39919211914» r9119»: cf the 1121921311 pro-inst: ms 11919.1. In mimce t9 the gamma {09.1.1111 (I) , when n a 2 1:19 pmdncte were 91919929ng ctflm- 5.19, 99-91mm 91911-39, owl-39293131 61919319931199. «299912.19, cs'clcm‘og‘xmmz‘hflrgiic 9.31:1, 9:13 p110: 59119 . 8939:! 919011 the 99994395111199 of 9:19 121119 or bisesy-vshspmpanefamfl pares-21:29, the mafia of 9.195, on. 3:: 979911593, 91" 99031 of £1999 prof-acts 11.9 m $921993: ‘er-i 74' .fl L‘U‘ ilk. “us ., ...- -n_a, 1" 991119;: 1313:2919 1,3,2 mlopmzrfl 921102199 1.33 cymhpmm’l 939199.11'531919091‘13939119139 0.21 cyclopmpmmwfiaoquia 39:19 0.095 937303133110 trace It 31991;: be 3191;1th 9.1!; 15191. in 190 91591999 99199911,.11119 91-03;: of the, perozziie deem-999991119 accmm‘ood far by the products 9119911. Farther, 1t 9111 be noted t‘emt there we obtained 67;: of the theoretical amt or 993991-0959. 931199169, 9.11:3 213 of £19 flizeoretical qmtity of cycle-- 190991 mummnmmvlaw- 5:214... cs.¢[>c1 o Dice-Q 399.11 but eczema-.119 929911919 of 9:93»;11911991299993119 9:219 9919 93.99 pres-ant (1919.1: 5"; 91’ the pro-2:11.. ”19). It. 9111*" ha not-92*. tint the 1m" '5 mum of 119-199 91‘ when dim-21.59 113111119 199 9:51:11 to the 31.21: of the [ 111111191 01' 210199 of 9217,0113 9.112 eater 1119611991. T19 1199 99991119215! the 9999. Phosgme me also 11 product) howrer, it 19.13 999911199 in raw 529111 7191.1 {1999 tins: 0.121 a.) and 1919 99$th 9 111119: emetimmt. 11919911199091.1919 was 9199 a 13:91" mention what, but the amount 19.9 mt quantitatively 9991211191193 ,. although attme ware 913129 t9 (3:: 99 . 139 olefin m 991991.91. 1.11 t; 19 influx-9:3 999993 of the 999993.911 9119999, no: 111 the me or the 99919119 1:99 99999111 . This is gum-3.9.1199 119999311913 119991199 it datum—mates that %e 93111109113291 £1190 191719-91 rammed 1“ 91991.93 and 91:} not 1191119139 to an 91.1.3.9. 19411991. The 199119197 91' ti. 19 19991919 9111911199 in this 0999 _, and Lu t: .1999 which v3.11 be 91991199911 below, 199 emblisim b: an 9:191:91 55.10119 93111119- '11 cf mch, and than 999er of their Wlnred spectra. T2919, cyclopmwl 93591179 m pmhmw by 11119109319999]. cunt-121991911 of cycle- M99, and its 1:919:99 9399911911 1119 £01131 t9 be 199111-991 with tint of the 03.119th pméuct £11111 $119 para-1:199 99991129319199. fixings-owl cyclqmmcnfimxth, a new 991W , m wagered by we Meyer'- 11111599 reaction 91' 91931919999911 1:999:19 with Wmmpemcatio acid. M Q $33033 W W Tint this an the 999901993 obtained is mead upon 1119 91mm 111913919, Michael: equinlant, and 111319199 3319991191. This mm 299 an 1119291199 upmtm 19111921 no 199911991 91911 tmt of the ester obtained in the 9.990239931111911 o: the 5199995119. In the me of format I 11-51919 :1 a S (bimclolmnnni’oml p9rozdfi9) , itmt‘wnd that themcumvmummmmeuflqmtityto these obtained an the ciao 1199 or biacyclopmpemlfml pas-92:199. 03910119931 931191-199 1111:! 99111911 91999 W the 119.391- coanoumb 199119199. B7 The ammo entwined and mm: quantities m as follow (1:93:39 upon the (lee-mating or one mole of perms-ma): Mahdi?! when 919.999 1. 37 cycloéamm chloriéa 1.53 aye lehwrfi cycleémmeeafiamlnm O . 2.2 «£1.01va acid - trace plmagems men In 15913 we also, 33310ng was I. {211102 product. flm we obtained 93 .m‘ of the theoretical amount- of carbon 91:91:39, and 753.553 at the rammed. mm of weloiml ehleride. mm tom quantifies or mmfififlefidamabmmwtfiwmtotmme detected. A [2311 ”mm: a: cychhammflowm acid w W, but. not in «mm quantity to We reliablym W. ramm- m was also 9 Met, but. its quantiw nu not «mum: rho Womemetgain mmwmimmm row by eminent: or the 1.9mm spectra of the 1mm new with than 9112312396 from the 1592-92199 99mm. 09.91....” On @619me In this particular instance, the prefix“ minted accounted for 953 of the mafia exam-sad. £23 In mime to gamma twink; (II ), the bimlicycliwcetyl paradise, the products when n a 2 were qm‘iopmwlombimrl mlograynnmcmw, carbon (1103:1110, cyclm'opexmcetie 9:91, and pémsgam. The armmta of the” statewide detained {mm a»): 99901990111193.1133 of one mole of parades-.3 me u fallow: 69:? 9.1.1.;- .233.” carbon 91:99:29 0.35 chlom‘opylw'bbvl cwloymmnmmfiate 0 . 5-"; cyclopmzxmaecatic new 0 .6955 pimegtma 0.001 It 9111 be new 1.2m. only 9; or 99 {£190th amount of carbon diam-1:39 m mum. Hammer, 3;:: of the temmucu eater ma mm, and the quanti‘w at mrbcm Cicak‘m evolved and the 1:;-mat of actor found Wed very well. About £135 cf the pram“ obtained as cycle. grommet“ acid. Ea olefin could be dotecme, 9112er an the reaction mm, or in tho mucus trap. situated in the absorption train. Thus, 1! a mlnmlmrbml males]. as formed, it did not W to n mwzmun. moi-storm mwmmmasszorunpm. amend. ItWWbemmmad $531319qu m’ unim- Ln fiat no chhrimtcd what was detracted. 62mm fraction-u sum of tho mum mauve (appmwnmly 823% m 619111199) Mari unwwmmctmma 09.9912990ng Lathe infrared. emu. mm no team in the various traps. Tim, 1%. m cE-eciczed um mmylmml adorn-a (23.1). 57°) m net t precinct. The com- pound: tint were obtained fire again antahliafied by ammonia and direct. W of Wm wen. >913:an (21-24224 -- DeafifidiiI-‘Q In the ones 01‘ tom II where n «I 5, (1313939199meer per-wide) the who!!! obtained were similar in type and q'mntity to {£3099 obtained from the c3mmpositim of 12199391399339.13me peroxide. “PM, the follow- ing NW and fimir antitiea ware fame m the deemitien of one 1min a: perm-21:29: enema dioxide wickets-3193mm chloride cyclohmrglwrbkvl carc103‘3mammé‘bmwlam cyclohmmcatie acid Them Meta 99902de for 91;? of the 1293912199. it will be noted tent 89:15 cf the fixeoreuml camel: clothe and. 523;: of the 919993.91 cycle. hwlearbkvl ci'loriee no 013911391. :13 ester aocozmtmi for 3 3% of ma precinct» Manama in: ngnin 631912131 3:: very ml). qmntitv. Than products we eotabmhad in a. W similar to then described previously for the cum madden. The eifiemme in the mm of 9:9 mm thnnsmmmnt: Rimming. Oxygen ¢ 5921. ---o- 1.: OW . :29 O .. 08,99.O mo ammonium a: bemzssd pawns in dilute carbon tatmchlarida amnion m 5100 meme. Surprinm ea 1% my am, (Smite the large 99 701m of literature! on tho (loos-179933321921 of bonsai. pcmch , no cm;- - halve Band-y of €15 p211" not: from non-irsfiwsl docormfllfion 1.11 carbon tobaciflmfla’s has been roman! . Ins {magmas am! Emir qxntitios mm fmmi to be as follow (hand on tho émmsition of one solo of pomdfla) ‘ carbon (23.011619 L725 ciao-robmsm 11271 poem bonooato 03:3 1 bowels acid 0'03; The“ rooms! account for £12.75 cf 121:9 pmdfio. The am: a: chlam- bomm and wow 13.101.211.129 mm (1:;-3: and 85.5: respectively. The actor 0.3001th for 23.52: a: the poof-sou. mongoose has also prom, but again in trans qmtimos. It will. also in Mod that tho est-mt of bonsai-o acid ofitalnod In: 5:19:11. Tho (smut-y of calories anti ester 8.3:.“663 mmbly vol}. with the ammo: of cameo (3101:1629. Tim mine“ were Wad as boron (5..s., synthesis mi comparison of the 1m; «- md spectra) . 031101-011me in. oomsrchslly available. Phsml bmaoata was pro- ‘Ww by mailman!) of phenol and bwayl chloricio in a basic Minn. when bimyolopropanofowyl pmrirls ma downposw in carbon tetra- chloriés mnfialrfing an tacos! of 10.13119, the principal Want us cycle. pmpyl 11mm (mum in ’1”? 3133.5, but mmabtadly 9110;114:3513 in highs: yield) . filth-or organ-1o products pmsmt in ulnar qmtity m cyclo- propyl @1101?le , eyolo'gmpyl cyclapmfansoafiwxylats and cyclozmgxms- 1:11.2th com. 1110 “mom‘s or the 10:21ch was 11-532.me by 1mmz~sci (no éoublo b01115), 01mm analysis, and preparation of too W ”l " warm which mo oar-‘13s: to} to mslc 1v-xmooalmo 91.11: as 5. 3. Unlils bmmoyl pmrslafis, #11331 IVs-1 (t'3~_- :3) $013.2?sz £05313"?! 3 Q3:- “212.3. totivo git-11:1 of bmzoio acid moo doommsoo. in carbon tfimzi. 1 2'12"? 9 mum-1.1.1133. 011.39 to?! 1am“ ~. , b3 oomlopmmmi’omrl pomfic‘s c.3152 not give a tromtibstlvo stairs of 1:;," .555; woman Mom'Lo acid. ms Q.wrtity of acid m, hmor , considmohly moms-so. at too ago-s- .» of cycle 1:13.171 1061:3321. Tho results we as follows (based upon tho dooormoition c! one mole of Wm): Em WWW mwlmml 1333.239 0.231 cyclopmmooofl smwlio ac: i... 0.62 03-01:); .mpyl cyolo 51mins aoo 1440)::th 0.0;; msrofors, 2.5:; at tho thsoro .loal mom’s of loads, and 2.11;; of too £23900 ratios]. amount or sold-- mo 0232mm. appvwoaflmtoly 1.3.310! tho product. no attributabls to «tutor. Sims those motion: wars miss out in Coal-so tubso, Win for carom-L also :13: is was not attozmtm. 1331963339 mo also prosont; how-saw, its ass-oat was again 324.3... In the moo of the at. so: biwlfloxclicfomrl and soot-fl pm‘thoo, mauvo possum malaraoo was not xmfomod. Hmor, it me quinin- have]: muons toot tho 1:13.710: product as the caloric-is correspond- ing to tho dbl radial famed by dooowosition of the appmpriato W9. mu W 13 based upon t: 9 foot that a oonsi: Eomblo amount of carbon dioxide 1»! wows: when moss autos-isle decompose-x3. Fur-1.211111113117213, at the conclusion of each Mastic smart-soot. (dissaossd in tho following Motion) an infrared metros we run on the motion mamas. Tho sotor v; 2 J and ass... 1 11-31-1111]. b...1.-:?11-11:13 1:21;..111'15; but 57:23.1“ 5:; ccnpnrissn Isifis 56731-3 63-13! stroking; buxom. 11:12.3 5 or.” “11135 {do-511.1953 Wow 1.1.2.1011‘3on-m moms-t 1.1 11.115.31.321 tho sot;- mr the 11:13, but t: o 211:3}. 'I‘ims, it no: 313:1 tot in ms. 1 cos-11 £1414- .. 3, 2.3.2195. 011:1, the mjor 11mins. not; 1’21 on t‘: .o monotonous coco; 1.112331.th of to various soy}. paw-does wars cannon 63.011.11.33 and 5.13331 offlorios. 23:3 ens «mm-2191.16.11, that or his. ”filo mmymootyl 96:13:13.9, in much as corn swear.“ enter an pracE-ommtsly form, to: 901m1st analogous to the coo-s of bimbo-11v).- wotyl pom-Aids roportsd by Bartlett and Lei-“flow (71) . 11111;; toms! tit-s follmzingp. ocoon! £2101: to 6.500329381tifin 02' um 1311:: 01‘ parodies rm..-.a 1.12.3? -:r- was» m.-. bmwl chloride 0 bsmyl phsmrlncousts 0.325 1’3. 225.110.15.503 of tho 2-sco...11:1r1 .3312»: of Various A6511 Poseidon m kinetic octet-muons oars porformd in (35.11.115.19 comm tows.- sacrum solutions, the 13:23:15.? of 2113210211119 ranging tron sol-0.1. Tho (Esconpositim tom tin! 5.2131: 02113 or 2.1.5 “1:112:13 oqntiom #4? “If . 1‘63 (F) 0 much upon fluteggzu‘slan givso “c3. 18:1 0’)" 1- 11:3 9* 103 (Po) (P) «- mafiatim cf? par-9:333 at ting-3 1:, (P9) '- iz': witia’ csarrzzaz:z’;'z;~e.iz’;.cn of P€}I‘fli‘rfif;:9 k; a $3315 mu’ar rat-a crewman 5-9 In pmctica, the rate or dmgpmranoa of parozdda ma follows-:2 by manti- mum infra-‘36, using t a hand at 5.65 microns. in wmmle of the prom. Bum 1352mm in Fianna '1. In every mo, the base line- we manly emu!) ..shad baron men sax-1&3 ef ammtzm. The rat: cmmnt, lie, me then calculated tram term laast erg-swan 31099 at a plot, of 105: I?) um i- (we Fumes am: 9 far t;m w]. uplota) ltd 1- «2.3 £3.21: Activation nga m calamted via the intagmted iffiimlm " equation: 13ng :- o~-r~ é- . 2'. ' 2.)- :5 The plots of leg kd vs III for me warm mafia: aw in Flames 11 to 19 in 9.3 La imam In each cams, 12:23 activation energy was «imbued m the 1% We. Mp0 of {3'10 plat. E: o «9.52 x (31.9339) 3. o 1.98:? calmdaa cams“ mic”: m enthalpy of uctimtian, A E , m: Mediates" from the falloumg equation. A I!" I “Ea-Ti? The meropy or activation, A 3*, m 031th from £210 Eta-1n; equation (32). .52 Q; u :25 0m n mu 3 \ H :34,” cm, H _ .sdn ma n p 0 .cd: Om u 09 :5; ma u m .2? o n g 98.33” ca :flucwamfiw: mm.m mm.m mm.m mo.m mo.m mm.m mm.m a _ A _ J a _ ow: m m a. m I4 mp a . . Fla; fll. fl. Ill! r1]: hill. .o omit pm mnfinohom Hmpwommcdxmnoaohomfin Mo 2033098009 no @0323 on» mswcflfinmpma ca new: €5QO vawnfia m>333cmsd .5 mama 0: 0m OOH uo IBS‘FIIISUBJJ, was sad kg? A 349/3 - A 3721' 1%.?! O k' A}? T or AS‘ a 2.1-“. Mg F3? .. .n h I- Planck's amount, 6.623 x 10 erg second .15 .1 k :- Boltmg- mint, 1.330 x 10 erg degree 3 molecule The various an amount. are listed in Tables 15, 16, md 17. Ta. activation margin, Wain“, and entmpicas for the W peroxides are listed in Table 15. who an. own show that in the an o: the biélicyoligfoml) We: then m a study increase in the at. or dwamnitioa u the mas o: ring urban: Mun-ed. However, it in mam tint the a“. bow to level of! in the man 03-0, (lea Figaro 10). On tho othcr hind, tho mios or bimlicyclimcatyl per-oxides showed an “singly fut an of duoupositim tor bismlom'opnnaaootyi pat-oxide, and a m an. nan-1.1 don-suns at. for the 0.4:, substituted perennial. Itilwidant treatable. 11mm that the mMcmtobo Wt dependant upon tho actintim amiss. Especially striking in the M “It then am about om kilomlorioa per m1. difference Wen Wimmfomyl peroxide and biacyalopmpmmatyl peroxido, em norm and mum (inhuman; mm, nupootivoly. Although m a striking in tho aha" Won, scram]. maximum or the who in Tabla 18 m that than is a genera, it slow, dunno in satiation margin at tho who at dacmitian increased. The activation mg for the «cementum of biacyelopmpanafoml peroxide (29 kilnmloriu mmEE ERI'E‘TIC PM; sous-mum m: ms: mamwsmxw or am mmummurzm. Pang-533 (303'). Immature °C. k; «e .4 x 10" mloprowl 63 0.255 mmml 7° Gdafilm cynicpropyl 70 0.5fl9mt mefl 7‘3 1.19 mlobutyl 65’ 5.81 cyclobutyl 70 8.33» 3310me 75 15.2 03131013me 130 1.25 cyclopmtyl 12.5 2.69 mmmtyl 53 14.91 mlnpmtyl 55 ' 7.1;?“ cycloham 333 2.57 «gunman 340 £4.97" cyclohaxyl 15 10.32 mhhcptyl 35 8.05 oyclohaptyl 230 15.2% mlohoptyi RS 13.}; puma.“ 70 1.12» w ...L A A __ ____. +—-v-—-——— _ w .—__ —v—v—' v—w wivw“ .Althaugh mi 3 mlmlkmefoml peroxide, m1 peroxide no candied and is listed for 00er mom. “The ”mg: of two runs performed upon diffamt pragmatic!” of peroxide. For t complete compilation of all the kinetic at... Mama should be and: to the Appendix 91' this thesis. “"1111. nt- oonmnt m detained with ma iodine present. 97 Titling 15 KIRHIC RATE cmswrrs F535! TIE DECOITOSITICfl CI" 80533 cmwwmcm PFQCDZIU'E'S (303.00.). 1mm” 013. k,‘ an.“ x 3.0. mlmpfi 1h 23 .6 cyclopmpyl 25 102.1. 670m}. 65 1.5"?» A miebum 70 2.0” mh'bntyl 73 3.96 W1 65 1.97 mmtyl 70 3.12” mmtyl 75 um cyclohml 6.0 1.10 ayclohwl 70 F 2.87” 01:16th 75 3.78 .721. "mg. of tun run- performed upm aurmm mum of peroxide. For a mint. compihtion or :11 the kinctio an reforms Ohmld be and. to the Ammdix of thin man. Log (P x 103) igure ‘i. not of 10:; (P) versus t for the Decmposition 98 of Elise}cloputtanefomj'l Peroxide at 1450, 5'00, and 530 b. 0.99 0.93 lilLlllJ 15 30 hs 60 75 90 105 120 Minutes LOO (103 P) Figure 9. Plot of log (P) versus t for the Decomposition of Biscyclobutaneacetyl Peroxide at 65°, 700, and 750 C. 99 M65 *— 0.h5 L... 03h0“"’ 0-35 - O.32 "—- J l l IJ 15 30 h5 60 75 minutes 65° 70° 75° 90 100 mimic was ccummm ma THE zrzcozegcsmss O? VifiICBS ALE. stamina: AT 70 C. cyclobutnm 8.3 Mont-nu 35 .5, newsman. ’2'! .5" cyclohoptm 79 .5“ mumpymmi 1200.0” eyelopmtylwbiwI 3 .12 mumtymrbmi 2 .o cyclohaaqlcubhvl 2 .87 W::- m;__- wi__: :i “w:: ‘Exmpoum um m m. irrhmiul mum; mm at.» were matured at hO-Z'JJ . ”Whtod ulna frog the Arrhmins «nation: some]. at.” are named st 354.10 .- mmohtad nine ”33 the Arrhmius aquatics; actual rates as. W st 1:;-2; . 111 $131.11 13 ammncs mmama, artists, A111.) :1: wens rm vs-s-tzcus Arm Pfiiififij-ZS WL—E— shut: :7: is: mr—W— W meido g s (330’) ' 133 H 3 A ,_._..._. A 4 “M .._ ~43 A ...___________ w: wfiw _. ~77 ‘7 w—W ‘r w “w ‘w‘ W‘fi 29.3 1': 0.9 23.3 '5‘»? t 2 27.3 t 0018 23.5 44.2 t 1 23.5 t 1.0 25.0 05m 7.4.: 2 2507 t 101 2501 .301 t 0.8 22.0 :2 1.5 21.1; 44.6 t 1 5 D O O D“ 26.14 t 1.0 25.7 4-? it 0.5 33 I 0:... {Day 27.0 i: 1.1 25.3 ~3.8 t 2 25.1; 1!: 0.8 25.? 4.0.3 1 2 17 15 102 Figure 10. Plot of kn versus n (n = number of Carbon Atoms in h 11-1 the Ring for Several Biscycloalkanefomyl Peroxides. "qE p. 103 m 1301.), s.- abmt tho name :5 tint for the osmium of bamoyl We (71) . Also, tho lotivution mm for the decomifion of 1:31:1le peroxide W wall in mmituéa with fiat of bmmmem paroxmo‘ reported by mum (71) , the values being 22 and 23 We. per ml. respectively. Wt also found that buphmhootal par-odds éacmmd u an at m a. balmy}. pemxida did at 70". Th. “tuition in apparently the mm mm uncyozopmpnm- mwlmmcchMpmndumm. Intho um Cindy, Bartlett (m that bimhmhaetyl peroxide man-want a Wm an induced ammonium 51mg an: tho :m mm mum. In an W13:- mm, 1111an told an & deconvolution Mat mien furnished the WM 10m 1..., it m an unwanted mun. Hm, umlylil of the nut». dish chewed tint thongufmdo of the tonic mummvuymnoomndtofimmmm. 81m. WWmMmmutmdmuthmm this «new. it 10 pensiblo that : 31113.1” type of ionic reaction my In" occurred. no atuwt no and. to mine the data tor this] m, M :- rm that the unwind. of this motion as not Swot-taut mm W with thnt a: $223 rm M1031 motion. It m interesting to £1121 that film My 0! wtivatim ulna. m menu", and not particuhrly 13:39. (3:13: in tho men of bin- Wemx. Mnmlopentanaawtyl, and bimolohmmonyl Wen-did mum-approach ~10 mmpymu. “mama m 0111: in tho mum mmhanisa, $213.ng mfivcm 102; W in that. m an: be “waisted with tho relative the of cabin onlmt use. inch It: be mm» A: can In m in £32310 1?, hiscyclomopnnufwl peroxide dscmpoaod my m1: u M u bmayl panama. fiche mot flat 1%. rate or ammummoor whommmtmlytha mutt m in 1%! MI, W $21“ Wed ammunition in: not taking place. I! it had occurred, tho vary oxfloim radical scavenger, twine, mmvouwmntomum. ' The. n u om; mug-1w hm tho mm or (ammonium or the Mmudowl peroxides and cm at” of abstraction of Emil-agent “on 2m manna W reported by frown-Siam tad Stacie (pg. 68). War. the W155! batman the at" of mmm or m WW1. parmddn And the decomposition of mica. “1mm Minted bismuth W by Drainage:- (psgo 6) 10mm. mmmuunbodmmmmmnm mum on nebula. P. Pmpoud new for tho Mnemoaition or the Various 4:71 Pan-mac“ In the may or the mnemoniuon or variously Wi‘hfl'fid W puma-d um negated that alumna repulsion hm tho hm“ mp. mad the peroxide. to dampen, and flat the Minty of mo Manly tamed racial. had no inflame on the at. (36). Hoard, thil mention predicts that other: alleyclio marl par-oxides 831mm daemons tt very nearly the was rate. The kinetic: malts 1am in thin thesi- shaw that. this in not the one. If. m swarm from ‘1: ammonium rates of thn bianlicyclico fowl madden tint they ganamlly temied to follow tho order of Wm awn Man found by ‘i‘mtmndifickmm and Stacie (page 68). The only exception as that. of bismlapm‘anafom'l pamzdde, which. damned more daily {m biscyclohemneforwl peroxide. Also, than 'u . (2°:me pamllel 1'.er among the bianlicyclimetyl mum than cmrod to the rates of decompositim of various bin-‘zmitriles Wmtod by Oven-barge: (page 6). The aotivatian male! shoved sufficient divergama to be important. This mid not ban bean mmtad if 1229 rate: were controlled solely by fission of tho oxymn-ozq'gm bomb It 1: firm that. mmm'a attach or group. atfiachacz to the ~04)- bmd would inflame. tho energy required for its 11381621. 2h- cyclo- prowl group 10 olaotron-‘dthang with respect to other mm group- (76), and would be W to slow down tho at. or «amputation. Til-attest, m, shouldbcu muon- («mum-mm mm W peroxide on]: deemed its mic of decomposition by about one. but). W, in fact, the difference bum n cyclopropyl ax: a mum amp 1.- m w pom of in. It mid amt, We”, that tbs rate or «SW-incl: in neutral)“, in put at but, by mother procu- u won; an ItMVO mmtyumommmnmaamflmmurm. 9 k1 5: o-g-om-st M 21130,. W EEG.- 0 Ru «0 CO. In othor words, admin. 3:; nor 1:, above would be won enough to exclude the other than holping to dot-groans tho so“. The whammy named mumtkémuldbotoomofk‘mdkv The following merino of notation. in {emanated for biocyolopropmo tom]. peroxide to «plain the rate 63“ and tho promo“. k k a, Druid .1... E911. W4 [Vilmoit Diufl. CG. /’ \ LD' . 1. j —--- pa» (3) D. O Dig-6‘ «mm W ' 11.0 (:4) [>100 o .6313 M DQ433613 m D4351. c001. (S) 'CCII,a Q 0CC13 WVWTT‘: :w. C'Cla filo moored decomition stops om mono“ in tho than whom. om: And Eon (77), in a moat paper, found no midmoo for induced doom- Union in tho fusion of bioditodphmlvflorfi pox-oxide in oommtmtionl as high so 0.”) molar in carbon monorioo solution; oinoo the We 1:37 amazon-1133.033 in this tho-sis moo “Ml-15' on tho ordor of 0.03.4332 molar, it 13 considered bmimla that 132mm: doconpodtion Groom-mo... Both stops {opiotxi in omtion (1) am No.33. ‘ . dotswmho tho 3;:-Lo o: 6.3::er ..tion. 3:333:33 (2) has too maumLmsz first, that a cyclomrl radical an {32-05de (wish led to cycloyropyl chloride} and 3930333 that this ra-Jioal 63:3 not. rearrange to an (.1131 mdiwl. Tho romeo poa‘moto 3.3 335.333 u'pon too ugmonto. First, it 3.3 £33.15 that. 153:9 formation of a cycloyroml raeréioal, n (Mfloult pmm bowuso of I-st—zuin, contributoo to tho olw vote of doomsi’aim. C3olopwp31 olrflorixio night. arise from a. reaction ouch as >60,- 0 6-31.” >1 0 C0. 0 G631; which Clues not moire tho excreta Emotion of no osmlopmpyl radical. Riot tad Rois (78) recon-3.3.3 (immtmtod tho unlikflfiiaod of such a omen 1n 9.:-31 pom. docowositima. moy daemon optically active biMou-phm'mobomfl pm‘fiflfi. 1n cam-hon tetrachloride and £92313 on the promo“ me very similar in kind mo quantity to than obtained from £2 :0 dooocpoaitioa of bis-@3133 fizhowlvalorjl porozdée. When-morn, aim: tho zuomoro-luphoxwpmpma comma: has Optically inactivo, throne tho other show-d 7.535 retention of activity, the chloride promo- ably had boon tome} by reaction of 336mm radical with carbon totnc?‘ '3 £30 mthw than by the roootim or no lay-low radical with carbon WehhrMo. (3330233432303), w aggrifa,” curator: 4. co, 3 a a Gang-corg; .» 331‘ m :2$11.3«arr-c:-maczza o «3013 . It. in «amides-ad that such evidence would also apply to the prooont m, can that mum-coy]. chloride, moratoro, me from 3 mafia: mob u depicted in mm (2). the fact that the ”lotion ms ova-y (31111“ when to. idea: of. n rodiml in o solvent. oogo plausible. 32mm (3) met: 1m.“ actor, mymmynotoominnoolvont ago. To! foot 333% optically active moxie?" give "to: in which the oval. portion has mm: conoiéomblo activity (79,80) comm that on. loop com may within a. cohort. ooze, possibly by a mom-“d momma. . mmnmmamm dotoctod manhunt-outrun: motion mu (2:). Almonw «Mmudotokmw Mums, than ofmmprobobhmmt, noditmldhkoonlynvm .1.an claim-“yield the Wityofooid protozoa-d. mum. mmmmt‘m Mflityflntnoidomubymottho mmmmuuwmmwmm.mnmm. Hui. on: ma “ particularly difficult, and probably did not occur. ntommtommmmtmzmw too-h“- oyoWomfl pmxma mold no to. do“ for .11 of the We (moot bimlwrmanom'l Me, which will be discussed separately Mow). 1:39 Althmfi: oonoidombly factor man bis-cyclopmmnofoml poroxtio, tho cyclobutono analog in amortholooo ouch flavor than tho highor mm of the om“. This can be moibod to 1min 1n the two-- mbuod flog rooms; which, 313mg: not no great. no in o tin'oo- mm ring radial, my still ho oigrfifioam. 0n tho basin of non- bomoo Momentum boom loréroaoa om, mo probably would have output-ad tho bimlopmtanofonm peroxide (and tho cumming cyclo- hoptyl compoum‘) to Giacomo mro rapidly of“ tho oyolohoaql analog (3].) . The mom for tho alooor moo of tho cyclopmtyl ooopcmnd is not apparent, but to W to noted that all torso of then porozddoo doooopooo ot common mm, 1111 of match on appreciably faster than tho caller ring Moro of tho tattoo. Biocyolooumcotyl porofido, and higher:- moo- or thio oat-loo all. dampen at m the lam rota which, hmoo, no oppmciably clover tiara tho «momma; biooyoloanmromwl Was. This my be duo amply to too not that prim 1:13:31, rather tron meow; elm moieti- on being mowed. Saoozx‘m'y 1:33:31 radicals no mo otablo than prism-y .1331 mum, and m {harem-o tamed moo coldly. mil pmiéoo mot-oar 8.?th for including the 1’0th 0! the M adios). u own 0! too moo-determining otooo. In tho can. of bimlobutonooootyl, biocyolopmtonmotyl, om bimyolohmmootyl peroxides it. one room that tho W no Wt mo noguvo, than for tho other pmooo. It my 3511 be flat this to duo, in port It loom, to tho fact. tint: woos ommmtivoly bulky We: would have I lam-gar oolvmfi cage, my a 31mm:- marina or the m “mum with than. ' The hum of Macyclopmpanme atyl perms; 1:19 was truly mfiaabln . cm has to W for tho warmly rapid dmemitian rate, and also far the fact that the pm as principally the ester and that :12 WW carrupoming to mammal a: a ehlorina atom iron 2.2m solvent. m War“. 2313 «tint-in: may for this docmsiusn ma my four khan-Jada per min 10.1 than the nth»:- parozdém (and swan kilo- oflnrioi pox- mlo loss than biscyclopmmmfonayl paw-oxide) . A antic- mm m not wt for 511 um mu. 1'!» when. mm above for ma otmr pm“ can radfly might the” result. provided one. :llowl Eat the cyclopmpylcarbinyl frat M1031 mutabfluedbymm, Wmmnmmmufint WWW tor mambmpylmrbinyl Winn (nae page 14). Thu tam Om an identical with thou about in the min“: Com. k- ge ...-...... (mm.- o R- «9 ca.) cage aim-gen mun-EL". [armada m wound of the“ flop. in particularly favorable because at liabili- utim at 3‘ law WI. This accounts for the law activation energy. It 10 W that E.- (thct 10, than cyclomopylcarbimrl radial) in mm mm .9 $213!. it (be! mt sums a chlcrim “on im- 15h. Wins urban mama molecules. Its only mourns, than, u a min. with mm mm;- (m mam favorable 111 process) in the eggs ta puma; ways. this mailman“: magmas far all :23 observed facts. It. 31:01:14: be hater: that Ornamarger (15:) baa «plume: tin»: rapid dazozzmaltion of CH: 5,313 l [>»?-u-x~9<11: . radical. CE}? 0. 2:15ch Winn Certain cf these aspezimta ware directed tom the synthesis or dimlopmpyhcstic acici, the law-mt. being to flu»? the dacwqhaifion of 3.“ woman. '17:». mice}. than yruducw (diamlayromiwrbizvl mused.) mm be tho can! u that initially taxman! in thc ciflnrmm of (11¢ch pmpylmflm. The mfizaeia m skis-tracked shortly More 1‘60 mm booms. W Iya‘m (alm‘iy dismissal) semi wruv or prior Wampum. The m‘dmois, :5 far as it in: canted, will be sumac: hm. naming-spy). km amulmwl um: at: g1 brmmwfata :‘m a Rafamtaky mama to produce ethyl :7 ,f: «.157: lapropylf «marry- 91-091mm!» 121 5'8 .33? Vivaldi. flagraimfim 043:5) . miucfim fit": lithium um tantrum (8.33:) and :rfiZragmtion war platimm lad to x.‘ on 1‘ I;_ 3; Wk) ‘3 A ° A H . a-cn ~cu.-o-c-cxauuiflfiil ca-cnaucr “1-- anew—C? FH ' ; '-_ .au; ... .3J V V 7 F: V 7 523° 3.3-éicyclopm'1-1Wnol. win new cmm't-ar‘: to the 393mm (91:?) E21132: , man {1:;-1'01sz at 5:200 gave a 73:15: flair: of mat ms presume-3.. to cabaruca, be 3,3né1mlcmm'1-1-pmpem, as sham in the achm .. This olefin, on oxiéation 022mm Punish tin fies 3mg: dicgmlcpmm'hcet 1c no in: . L m WM” 01' cyclopmmmcazfiomldahyfle ma devilish: 3 catalytic aviation of cyclmpylombinol aver airy-copper on midst: with air y." good yield: a! the wta'mfis. . - and. 7 ,. 31304.1 ‘ :_ .3. ELL.) 3¥c° This mfim 1.3 mt! canrmive to large 3:35.13 prism-minus of the aldehyde than thou gim in tho literature (hi). 2.11 11112111111131.1115 01111111111111 uf a W311: on the cg‘clapxfiwu 2.3;; W 01111va 111m 11; ms 1:111:11 €311 £3~c3313pmia+23m1 (1m cyclm- rfim’l 3.11. 12111.11 3111‘. 11112151113 01:11.11) 1113 01:11:" ...sz by 11mm]. mum... 111111.13 to a mixture of cyclopmmnc 111:1 111:1 cyclnpropmmfizmvua 1111115 1 1:1 *1 Doggy-311 -&~p l>mfiog1 1 >031: 311313.;7, 6111;013:1191. 111.1111; vmwmd m 65.111111 11:1 1.11.91.13.11 111111 By 1111 1.1%}mep3'lwwlm v1 .11 3.111%”..9 act-:1. A 1 H350; .1 C33 W AWE} MW»: ta mko the cps-1.1.611 11:1. 1.3.1 113111111011 acid mo inacmlusivc results. 11 1: mtmating 1:111 121. mcgulopmfiw'aonm 111., 11.1.1111 prmm‘sly 1.: 1111 intermediate in we dckyimtisn, 61:11:01. 3119 mmngad product. 91-? '~ ~11 th-—~“u.k¢‘ 3.. :19 premem £1 .121 1'." 19 9.911993 3.9.9113‘119119. 4" mrmnleryclmzrne and 939519199191? ' ~19 11919 femmte be 2wmmm, 39399 11211-929191: .. .3119 911:3 l-cyeleprewléw 10119111114911, 1999199 ,1. 1119;" 1119919119 fer $1999 9911911: 19% 11119131991191! pro-$119119 were offer-9:1. 2.1119991199....1‘1391‘991p9rm'199wrepm9912111191111.1119 Max:199 by the fame: ( (1: 21..)a 93:99, 1, and I (3:1,)n 3:31,], were a a 2.7 9.1111 n I- 22-53. 3. The premcto 11115. rates 01’! 91909939111011 for 11219 (29991911 19:! any). 519901119396 11199 deterrenm‘. £111 91' 3:9 69991111991111.9115 were performed in 1313.111... 092.112.1323. in carbon 199991912119: 91111 followed strict first 99:191. kinetics. The principal 3119:9999 free (3130-, a 111 9.13. 99999 but one were 99.111911 919x199, 9119']. 9211911139 (7131), m1 lesser amount. of eater (29:9...) and acid (28-0 .3). True: 9: 999999119 were prefixed, and 11199191191991.1311. m formd 1.11 large but 11.193911919191191! 9911111119. 19191: R was «(31,, the enter an the mice- product (fif‘f), 911112193183. we detected. In all m:- 911;: of the pee-991119 1913 4999.111 1:563 for and R 131119911199 its 3119991111 integrity. 11111131911119 9912:3198 9f the products we synthesized for newt-on. The relative rates of decongeeitim of the name 11919121999 at 70° in carbon 1.999911111911199 were: a I 2 3 is S 5 n I 2 3 h S k I 3.103 1.?9 2.73 2.535 where hwy]. pemiée 11:19 n 1111119 01' 1.13. 371111199 were determined at at 1995*: three 99991191911199: , and on 6119219919 31919199. T119 activation «191-31199 tbr a In 3—5 99:! n a 31-23 119.99 9.219111: 2:5 1: 1 91111991911199 per mole. 191911 a u 2, 3* m 29 11119991911193 per 9:119, 1.91m: when n d 2, it. was only 22 1911099191999 per 11:119. 11. The 1999:, 11119139919 , 9119. 91111113199 an: 91911111190 of activation m 0.11 eminent with A 1119939111199 which included the formation of an my: radical a one of two rate 9999.919191- atepe. The reeemnee my 91' a mkmpylmrbiwl 1119111991 93319990 to be significant . 5. Several new. smut-168 were 1199519999 in commotion with the perm-1:29 work . The” were 95191991193911 10:11:29 , 93191931992151]. cyclomeyzate, mumpylaareinyl cycloprommacetate, thlepmpeneetimel, and eyele- Wwe’zyfie. 6. 30991111199119.9999: metim 511199191113 mimpfl «9511111199 99W were described. These included an 1.191909% 1991121991- 01’ 91.191911 W, the prepwation a: 1,141.19y919pr931y19thylene, 9112911 Bdfimlomwl-W‘Imemiomw. 111m. 3 .B-dicicloezewmwlau. t3 I . 65mm . 3 3 n. ‘ - b ’1‘ ‘ Wi'c . Q‘. “baht-.1 CLifixu 117 Ln? AW}: C‘. a.“ 10 C. G. 3811:5219! m 5. 55.3391. J. Am. Chan. 903.. 1:;-y hi: (I? 2)o 2. J. 13. am and v. c. Chm-barn, J. Am. Chem. Soc" 13,, 5031: (193:1). 3. H. 6. Bram,” .... 8. Fletcher, and ‘1. B. Joiamom, J. Am. Chem. Soc" 22; 232. (13.3.1). 1.... J. D. W w P. H. Limflne, Jo A30 Chm. 506.. £71. 12; ~11 (1324. I”). 5'. a. 3. Ham and n. Sehactar, J. Am. Chem. 300., 25;, 1382 (193:3). “Th 'l . J. 1'}. 3mm and v. c. Chm-bars, J. m. scam. sac... 13,, 3175 (195.1). 7. Fr. Fichtar and Ii. Each, 331?. flhha. Acts, 3;, L30 (1923). 8. J'. 2:. rm: and I. nos-ma, J. Ami. ”hm. Soc... 1g; 3.1; (193;). 9. J. :3. mam-ta anti :1. a. 2m, .1. An. Ghem. 300., a, 2:309 (19:1). 10. B. E. liowm and 3. xanatcin, J. m. Chm. 500., 12. mm (1935). 11. A. Etc-aim, Jr... (mam-... laws" 5:, 571 (193.3 . 12. J. g. sum-1, Ph. 13. mm, mcmgan scam Imivmlth (13::c ). 13. J. n. Roberta and a. B. km, J. ca. 61181:. 3°C., 3;. 2509 (19:71). 12;. H. 2:}. 82mm ma :1. Borkcmaki, J. An. 01:92:. Soc" 13, 1691s (1352). 15'. C. 6. WWW fig... 4’. Am. Gm. 650., 75, 2W3 (13,353 . 15. x. as. (kind and P. c. (m, J. Inzi. Chem. 506., g m man). 17. A. c. Capo and x. a. Bannock, J. Am. Chm. Sac..60 ___. 2?“ (1935). 18. 8. Final, w. ’W, Ind Y. 8. Imtieff, J. M. Chm. 500.. .62. 1197 (19147). 19. a. a. 3mm”, m. .1... Ina-1.1m mg. (131023., 35, 333 (19:3). 20. E. H. Ema-m, 'Cr ’ Chlprim 60W," John E1197 and Sons Inc“ has arm, 19:... p. 1110. 21. H. c. M Ma R. S. ”0:753”, J. 5,3, cm. 300., 12". '.n‘-.- 22. Wang rm, J. Am. Chm. 893., 6’3, 21.57 (19$). 23. ”We Synthmu,‘ Gellmtiva Velma III, 3022:: H116? am Sons, ‘ Wt, 139” Yark, 193:. p. 221. 23.. mg... :2. 213. 25. m... p. 119. 2.5. c. :3. nor-cum and I. P. Cmmaam, PM... 5;, an (1932). '27. a. P. mm, a. An. Chan. Sac... Q, 135:7 (1939). 23. L. gunman, 301?. mm. Am, g2. 35*: (19:5). 29. a. march and w. a. farm, .1. cm. Soon g5, 591 (13%). 30. 1:. ant and .1. :1. Sam, cum and W, 10-11. (1936). 31. a. 3. mm m: rim-hm H. scam, J. Chem. Soc" 232 (193.3). 32. J. H. W m: a. 3. m, J. Org. (than... Q, $6 (195:5). 33. A. I. Vega]... "muesli Grade Chmfis‘a?) Lemmas, 0mm mi (30., um Iark, 195.3, 9. 25:3. 333. 30 '0 am. No, £9 2529 (1908). 35'. 0. Cram, 6. 3. Board, and A. L. Hm, J.- .m. Chem. 500., £31 35. c. munch, m, :22, macs-7). 370 O. G. SW13. ‘3. an 5mm, ‘nii Jo To Chflifi, Jo £35. CHEER. 3%., E. 53.25 (19339). 33. w. D. m sad 0. B. Luca, J. km. 873.6321. 306., 11, 2237 (13331). 39. :3. :«z. Royall, 'Advmcad arm Chmnatry,‘ pro-mam, km, 1!“ 303.15, 1953', p. [63353. LG. '31. L. mm and R. C. m, ”Systwmtic 1:.3mt‘1flcntim of ('3er CW0," John may and Sons, 1110., Elm: York, 19.1.3, p. 133. 1.1. G. S. Kim and R. Amps, J. Am. Chem. 506., Q. 2392 (1925). 1.2. w. J. I-Eickinbottm, ”imam of Manic famm‘s," Lemmas, Green am Emmy, 19333. p. 953. L3. 1.. F. Fin-er, ".Isz in Organic Chwflstw," D. C. Emma and: Com, Beaten, 19.33, p. 29"}. , 1.2.. w. R. Bane-is, ”Chemical Spoctmscow,‘ John Kiley and Sons Inc" .13” 3.9.5, 1?..3’ p. 2...:- ais. 1.. F. mm,“ mimta in Omaic (ilrzwaistz‘:.*',‘I I}. . 3‘1th and Emmy, Boston, 1955'. p. 233. 1‘5. J. E. Rahal-t0”. J. m. Chm. 800.. lb 29:9, (33.31). 4’47. V. A. $131sz and P. 13.1.3556, Kat'l. aim'lsory Cam. Ammutica, T‘mho .10“ 22."; """ (19:1). :83. H. B. Gottllab, J. Am. mlfi’flg. 5043., 53“" 7.2.8 (D32). 139. by. Jo mm 2?... m’thy’ J90! 3g. $1913., 21 325 (19: £6). 5'0. "Organic Smtzmwa,“w '1‘ 52 (133.3. 531. “firm Syntérmsfi Gollwtivs Volume I, John £1161 and Sons, 1716., 330V“ 301%., 13,36. p. 131. 32. J. Staui’f and H. J. Sci mac 1631', Z. Llaktroehaaqb 271 (19 .2). :33. J. smart, z. Easktmchwm, 15," ;. 3 (13:.2 ). 51.. H. 3. Han and J. a. swim, Inc. 7.19;. Chan... 32,. 3:32 (ma. 53. F. F. “lust am! H. '6. Fa. u—g‘m, J. Org. Chm-21., g, 1.79 (1) .1). 5-5. :7. c. Bram m2: 1. a. .m, J. Am. am... 3o... 3, .319 (3.33131). 57. a. A. Emsasllfl. Am. (than. $06., 12, 2'27? (19.1.7). 53. a. s. Phamach ma. H. c. .. m, J. m. Chm. 300., Q, 3.32 (1935:). 1'59. J. ‘3. Either“ and V. . . "Embers, J. Am. G: 1135... 30s., L, 3175 (19:1). 60. A. F. ”smacks-mam am. E. w. '52. Stacie, J. £32m. Phys" L2, 3:29 (1931).. I (32. 3.. 3:93“! ”7312.! am; rqm ‘ M‘fimm.’ 3533‘...” q: .131: (1;?2 C). 63. A. V. T013035? and. -.. B. Katmai max, '“fimc PW,” Inter- 86138106 “01155191.“, Inca, hill YOi-IC. 17?, M. p. 137. 6:... 11. Sm, Chem. 11mm, 11, 7S (1950). 50 J0? I. Lain”. J. A33. Chm. 506., L) 3:92? (175.1). 613. , 3233135316 J. T. 3.115335111, m1: F. J. $3051C, J. Am. Chi-9‘30 5°C.. 22; 1» 392.9 (12515 6?. G. 8. Hey am. 19. A. 1&1Ws,Chmm. Ewe" @3313} (1337). 6‘3. 11. Kawki, ml P. .. may: 1:, J. Am. Chem. 800., Q 1:333 (EELS). 69. G.- {ms} and L. 11.5 r, J. Am. {3..em. 306., 1%,. L711 (1935- . 70. F. G. 1" “and F. 11'. He 50, J. 1:;. Chm. 5013., E, 12.33? -(19 0). 71. r. 1:. Bartlett and J. n. Letfler, J. m. Chem. 506., 12,. 33:52 (wit). 72. J.” .. Leftist, ”The ammo Intaneedflfitea of Organic Chemistry,” Intermiama PW .3113, Inc., new tor .195’ 3:, p. 31.. 73. A. V. Totem? and“ ... B. Rem-shun, ho¢ 1 ., p. 8:. 741T a) gram and C. 7:313, II. 3.31 .Chfi‘a. $909, I?) 1.296 (1;:5)o 73'. A. V. 1'31:an and a. B. mam-hm, M. mu 1). 83. 7'5. E. L0)Mm, B.- W, w J. H. 9min, Jo Fm. ChMo’ fl; 698 19 7 o 77. 12s. Ise'i‘ar and c. emu. Jo moi? 30%. 1'2: 3941 (1‘ 17% r37). 7}." . . S. E.- ..ras..., J. Ewim, and 11. 113.3333. 5, J. Cr: g. chem, w 51}. F. 1.1. Greene, J. 3:113. Chem. 3062., ' 1.339 (19,531 . 5..) 7B. 1:. Lab: and C. Mia, 373*???" 331.15 ( 81.. P. 3. E. de 13 11am and P. 9.11:1:ertam, .11.? .2133. ..3c-c., 27? (123.3). 82. A. 11. Mai; and R. 0. Pause-m, ”Emma-him and 1Eec‘mmian," JcI-m Kiley and Saw, 1110., 25m: 1311:, 1353. p. 9:3. . v' 'rv «.9»; '12 H S .23: {...—J 12-1 .7“. ,.-."¢ "'1 A Lam-Poamm or: mo-nrmflmm 2:; mum. P‘E‘“‘L * m Luz-13425 2-3-.31u211: A? 63 a: 0.2 .“am.—~\u—.L -~“mu Jinn-n. aw I’m 1° .- 18.35; w. P . concmtmtion (3,41) s «- 0.3323731“; I cammtmtion (2nolarity) Po g- 1. 231.3 .-/1 7.26 x 103 mm.- t. . time (hours) mp1. I on. log Io/I P P1131133 102 Puzzle: 1; 1 11.76 8.2412 1.13.3 7.02 0.31. S 2 11.90 0.19975 1.13:0 6.75 0.330 8.53 3 12.13 0.19%” 1. a 6.343 0.812 17 a 12.31 0.123;.ng 14233 6.27 0.797 21 *Z‘Z‘“““‘“* “fin—W “11...; w “‘1 M w ‘ __:_ _. “‘2‘: m J k c 9.2 + ca.s::1cf""hm."a o 2.535 a: 0.23. x 10" no. A.“ _._‘_ A ##M m; w A.“ W __ v_ ——w “-v 122 32131.33 20 332;. THEWT”! 03' 31:32: 2 “mam? .2- ”232.1: 31022322: 2:122:23: 1333'; 2’: 70 t 0. 2° (1) 1., I 18.138 m. P a concmtmtion Eng) a 0 0.3473 Pub commmtion malaritv) Pol 3.h3¢J'1-1.h3110" min: £~t1m(2mro) 3”?“ :2;?31¥‘ ’ _ 52‘1” ”193123.193“ ‘2, 1 7.31 0.1.0278 2.32 13.6 1.13).. h 2 7 .83 0.371.521 2 .16 12 .7 1.131.: 7 .5 3 5.13 0.35335 2.61. 12.0 1.079 12. h 8.52 0.33325 1.93 11.433 1.03? 1h 5 9.235 0.351).?!) 1.73 10.2 1.06335 21 6 10.53 0.23.221 1.3.1 8.3 0.919 23 1 10.90 0.22927 1.32 7.8 0.892 33.25 k a 1.77 3 0.11 x 10" hrs.”1 II 1.32 t 0.30 x 10'. m. “ —-‘-‘-‘ -‘--‘-—‘ —“ “—A- #—— A‘ A A 3“__--; ‘A- _-‘ “‘5‘ t“ WWW—... ... WWW W ... .... w WWW... 1.23 02:23 21 ....czyasmr‘a or 1322110273032... 1.2.3-121. P220212" 1210.22.25.22 2wmtlm 21' 70 t (3.2" (II) I. I 15.79 022. P a cancmtmtion saw/1) t a 0.3.273 P3 0 concmbmticn molarity) 70" 2.9058/10 1.735210'330122- ‘3 O$1.230(h0ur0) ....u A _._“_. A . A... ——-_ ...-.... AA ‘4‘ —— 4“ WWW ,____ w ..— _._. w-V—v w W WV... w w v.7 '- —V W‘— sampzo x cm. 10: m P 23:10: 1.3 Punt» 0 1 6.32.. . 0.1.7181. 2.72 16.00 \S/RQ” 1.20:. I. 2 6.30 0.2.2.1322 2.322 132.93. 1.171. 8 3 8.12. 0.30331 2.09 12.29 1.0396 13.5 h 5.90 o. 2.52. 1.01 11.00 1.020%. 2:. S 9.29 0.30591 1.76 10.35 ' 1.0109 29 6 9.65 0.289320 1.07 9.82 . 0.992 32:. 1‘ CLGStOJIIO-I 1216.8. 015.693030110‘. TAR: E 2 2 EZCQ-WEI‘PI’L‘EI CF 313mm”: ~.Z.'E?T'£"32"£T'i’.. P’l’ZflKITEE I?! CARE}! 72.322101: 683111133133 AR 20312-23222 3.3333132? C5? 13313133 AT 70 t 0.2 Io :- 19.15 on. P a conconfimtian g./‘l) a. 0 0.33273 4 ,2: III commtmtion misrity) P9 In 2.1.5 3J1 0 1.1.5 I: 3.0 molar t :- $1.00 (hows) amp). 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R K ( O 1.22.33 :4 -f-2.-:‘3 E75.» :12." 5-" a: - Io . 13.33 m. o. a 0.293;; r... -. 9.731 z-ll «- 1.315 x 10 J mm P 1- concmtmtian Pu II- emcmtmtion t II um (minutes) i go/l) molarity) amp); I on. 103 m c canol- t ‘ W: 7* A. t W : _. -..”...— : r. 1 1.95 0.97:”? 9.35 1.322 0.67133 15 2 2.11 0.91.00: 9.».222 2.513;“: 0.53359 30 3 2.33.; 0.895.713 8.591 23.339 0.63739 15 z. 2.51 0.64771 8. 35; L139 c.5137. co 5 2.91 0.83036 7. .22 3.880 0.5332 7s 5 3.50 0.72023 6.912 3.2.91 0.51.395 ms 7 3.31 0.67217 6.2.. 3.25:9 0.51295 120 a 1.3.2 0.62915 6.233 3.1;?) 0.3.9333 13s 9 Mo 0.62090 5.95:9 3.009 0.1.7322 169 _._.__LA_ w w ...—.— ...—......»4 4—; W k 03.2.8 __A_ t 0.15 x 1.0“ um." II 5.81 :t 0.25 m. . _‘_ ..a__.. fir... w ‘— w W...“ ww- w w 123 223333.53 2'5 Ema-Emma: 0F Ezsmommmmorm <3er m CEJEE TEE-0001mm“: 70 .t 0.2 (x) .. ‘ . 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P I 0011120111....111 "I (g./l) a It 0.2752 Pa I- eunnoutmm n ( 13311.15. 13') 1'. a 2.127 3J1 - 1.29:: x 1: 111m 1.“ - 11:11 ( 11111111) ..s... ...... 4‘.“ Vw— v—w— W 11:11.1 1 cm. 1111 1J1 :1 1&0!- 1111 runo- t. 1 3.19 . 0.77833 2 .836 1.252 0.09750 13’ 2 3.31 0.7 77? 2.772 1.225 0.03319 3.0 3 3.3.13 0.731351 2.4333 1.1371 0.073791 63 21 3.73 0.70313 2.3152 1.131; NO. $1.51 90 5 711.01 0.679118 .1. 69 .5192 0.03 922 120 4*“. M 1...... A A... Lw‘ M ... mw‘A-L‘ _.__.._ 11......“ M11 WW W ‘— W —._.—..—7 w WW 1,. WW k . 1.51 1 0.13;: 104111111." . 2.19 1.- 11.21 11 m”::::::. 1121-» 31 rumfifigflwmfinwmm E? ‘ 11ft! “n‘ ,_ 11119111. ‘1"7‘fflf‘731r1-fl P135 r'r-fIv :8 ikwv‘u a: U4}. $1.5. ‘JJ (1“? «ML-5 1:41.114! .3. kiwi ..a.‘ 1.: 1.; $15.3" “$.41 ‘J .2: ”It. I. m_‘ls:18,l M7 "1"” 1. _f'\1 r ’L.‘ ...—11.1, (If: _ L“ at: and; at 4511;11th u-r " Minn-”'1 AT :‘N t 0.1 Io d! 19.1? r o communal 1:.fl) ; a 0.2752 , ... 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L ._— A. M .- _.... ...... “...“..‘m..- _. ...._ ___ 4—.— ww “..W W "V w... .._ ._fv___.,_.. _. .... .... .w 3.3-3:...313 C3 maneumnmm. ”33.1. '3. m 6.....33: 1.113.233.3113: 1' no t 0.1 (I) 10 I- 17.03 cm. 1‘ a cancmrtmtion (g./l) ' a. . 0.2733 ... Pn II comemtmfiion (mm'ity) Po I 7.363 all ‘ 2.63.56 3 3.0 min: t. a tin» (mamas) Mil. I cm. log 19!! r 1533.9 102 anm' t ._ Ah _.__ .... :1. F w ... WW .... ...... ... 1 2.23 0.83291 6.3.2.9 2.237 0.31.7927 15 2 3.00 0.71.39 5.503 1.933 0.23070 30 3 3.81 0.6353:- L.7;';0 1.63;. 0.22531. 1.5 h 2.52 0.53763? b.2951 1.1.92 0.17377 63 5 5.10 0.5233: 3.325 1.333 0.11351 73 WW k09.h320.55x10a * # A A... ‘._._. . _-...._ ..4... 44.. _— .....n. _.._ M 4-4 A.._ --... __ w W“ V w m w -—‘-' Vw— w?— w W w —v—.—,— ‘— fi— w V—vv' w v: m- 3: 30 rum mlmrw V” :5? , ‘H fiTe‘fin'r' - "NF-“NEE!!! *?:‘”~‘.-‘."?')1=."?F , 27's.)!“ 1"” "Ilfcvil'; «)Irfi; JQC.‘~‘ GO. Lily-'3».yld -. £1- ¢ b-v-u‘ “3p‘u.’0{ 3‘.)- -9 0.5"} FM“ -‘}I&ga':3 .- . .. ... v ' o . 31.7.77 7.3.3.0333103 AT :33 :1: 0.1. (1:) ., ...-......» ...-#235“ E S3 1:: :- P O mmflmtim (en/J.) a. a. 0.2738 J Pa O camcmtmtim (.nolari‘W) y, a 23.351 3J1 I 15.1.6 I: 10 min: t In time (:mtea) mu Ion. 105on 0 73,3210a 103033.108 1. LL AL M M A. M A# __A A. 4—... A A____. A..— .__._.._,. w—w “... w—W‘.’ ——-v—v —- . v—v 5.02. 0.52332 3.8537 13.00 1.13309 5.32 0.1.53: 3.1.01 12.00 1.03135 6.5:? 0.341233 3 .015 10 .70 1.02933 7.19 0.37372 2.730 9.000 . 0.9053 7.91 0.33227 2.327 8.000 3.0 8.67 0.29233 2.1365 7.57:. 0.87933 8!: 3.3:; amt-Low“ 8 A“. ...M A __. u ‘4 .w rv—‘w w—w—W—v—w—v w wwt w 1. . 0.72. t 0.1.7 x lo’mm.“ a 1.1.6 2 0.08 x 10 m. M 3.. it 11.3 7.3.23.3. 2.1 BEQTTGSITITI G? mmm 'W’"TG‘JM P Jams I}; 0&1” IMO; It“; mud” I136 A155: 0.16 1., I: 17.03 m. ' P a mam-anon im/l) .0 . 0.2733 Pu I mmtmtion mkrity) P0 . 6.809 3J1 . 2.390 x 10... mm 0 .- 7.10.: (mm) 8073910 I m. 10: 1J1 G On 103 an t _ 1 2.88 0.77132 5.638 1.999 0.29385 15 3 3.92 0.63792 10.5.39 1.6532 0.23.331 30 3 2..82 0.51.815 b.7303. 1.2.20 0.13229 L5 3. 5.0g 0.1.7916 3.500 1.210. 0.33377 60 s 6.85 0.39552, 2.889 1.02:. 0.1030 7s kam:o.o9x10"m." .. 1.01.20.15x10 h; .... ... *7 wwmwv—ww mu WCWGMCMfW nmmmmnntm ' 1.. 3.8.85 _ P u “an 341) . a 0.11;; .. rat-W Mt) 1,-6.01m-3o.55xm .1:! 1 cit-(m) ...-.1. In. Inn/x P 1.1110. ugrpo' 6.18 0.1.1135 5.51 ' 20.19 1.56510 $.11. am 5.21 25.61 1.2mm 1.50 am 11.61 13.56 1.11113 8.09 0.36165 my 11.18 1.33006 3.1.: 0.311109 MD! 10.82 am “PUD” QSEXKI" ‘k a 11...: t, 0.10 1 10‘s..“ - 33.6 t 0.30 x 10“...“ var-2141'- 7‘91. ~11 {-19 ~7~4~m may. a- 1. a W tMK‘W’W‘fi EkNMJJQk};‘ L"; if. “Lu?kl&mié-rz. lu-Ji bunch-J. “JJ‘JA‘l-‘(W’J m 0.133.731 TTAVRNLL‘. yr 25' t 0.1 (I) In is 18.85; P I'- meantmtim fan/1) a. II 0.1715 .1 Pa :- mncmtration mkwity) f, 11427.8 ¢./l :- 12.1.3 1 10 mm is a timer (gamma) Sample I 013. 19g 1.3/1 1’ aniO’ log P113103 t 1 2.83 1.11557 12.871 65.01 1.81298 35 2 9.21. 0.333373 3.612 18.21. 1.25102 30 3 £1.39 0.10539 .23? 5.207 0.759233 £5 1. 17.12 muss. 0.1.375 2.2.653 0.39135 60 5 17.73 0.9252. 0.31:5}. .33 , ’ 0.13733 73 “ a. *‘h" :w— *w‘ 4““ ...; Air‘” W‘A‘ ‘ 44* I"; 3W _: 2w .3 .1 J k . 6.32 1!: 0.5 x 10 um." I: 1.05 t 0.08 x 10 m. A. N “A - AA A .—..;.. Mn‘ “- ...A .1 w—vww WW ‘7 ._.___ W ‘ V. w "a ”a" '2'. 31 Li-ALLZ‘J .44 *1..:.** Iq_~a!..1‘ 4-1. p. .---- A, a”? ' .... q 2.: wtétfiA 2.1.21.1...3 (Alf .3742»... Lw..v‘t....: any...» 23.2.13 3.....5 IR {3:1, 135:! T~-u‘i‘-‘- WW— «.mam M moo-“w“ m- -m--~ Io . 13. 8; 0330 a . 0.171375 2. - 22.32 s /1 - 123.3 x A 1:" .Ld'w; 5.1,; (IA-,1. 25; P 22./1)13d 3.33.13.41.11. +2.1 fl P I coacJutra t II the (:Hnu‘tus) 3"} ° (1.) w‘n.d\1 3.1331 1325 1 2......13 1 cm. 103 Etc/I P 2,222.23 103 2.2128 t 1 2.2? 0.9222? 13.733. 554.221.? 1.735“ 13 ,2 8.535 0.21.325 2.223 23.22. 1.32372 32 3 112.2..." r1..3 1.311 9.3.2.5 0.96123 L3 3. 16 .91 0.2.2233 2 5:32 2 .22 2.22.3.1 63 5 17.63 222 ...:2 1.22:7 0.25222 15 ._ ; _;;__- ;____;;_;;;;;.;.; ___;; ;____;;;;_.;___;;__; ..A .2. k .. 5.95+ -_ a .11 a: 10”....212. .- 932 2 0.22:10 m. 2» 2...- ----u_m--m--w2:A¢-:-m fi-~~gflr:\ “45.43.. t, LL! ”wrath. an \1'”... q: C“, 13:... yfiwq tv'u m. ‘1“: fi' now—gs / mg». $JWW“ 4“...“ *wcu—“w-W It. v ...-wan... 31W f“ ' $221". 1...?» .fibJle-é.‘ ‘1'”: .1; A? J: 0.1 WWW“ '"~“i:z:;.;22.:.:* Imam-.29.... "-2 :2... “- “wt-:33: ram: Io O 17.10 can. P I {33112.15 ,A) a II 0.1332 P“ C 20* ”ninth“: Em"1;-f.tfl Po . 501,33 EA . 2.52:)” x 1041334.}. tn . ‘12-'13 (may-away) ___..__ 8... '33-..t -* ...“ v—‘v—v -v-- ... .—.—. ....v. v. m 7.,“ ”amp” 3 I em. 155 10/1 1" Pat-22.33 13-; P823133 t 1 5.30 0.52222 5.2.5 2.22: 0.32239 13 2 5.33 0.3222 5...... 2.26.3 .32.;- 32 3 5.2.3 0.2.2122 5.1.23 2.2.27 0.33527 1.3 1. 5.5:. 0 1.3929 5.1.33 2.1.2:. 0.313223 60 s 5.21 0.2.2.21. .3... 2.327 2.27332 73 6 57.71: 0.273.“? 17.252 2.328 0.3’ 98 92 7—4 ...“... wflw~ 1: .9232052210‘; ulna.“ _ 12.23 TESL? 31 ”NAIR!” rm M I Wit. QT’A‘" “'3‘” ‘H I" ”'I a: .‘2.lw-r J vfiWbI G’: Uhdnflzfl‘ww Mi.’ NU in“. - i: I: .4 I2: 22:22 E'TIAC'AEI 2 ?'I016.1 (I) 1° 0 17.10 on. P 0 concentration (g./‘) n a 0.1212 F, II concmtration (mom-21:3) 9° 0 6.2321 1J1 I 2.736 x 10 4mm:- ‘1: '- tim (Bacon-:23) “A A...‘ A 4 ML...“ A M ...—......“ m ...“... A -—A L“ w w L—w WWW ww— w W w ...—... 39mph I cm. 103 19/! 2 anlb' ' 103 Pu t 1 12.126 4.533237 6.3273 2.57? 0.123755 15 2 b.6h 0.535L8 5.237 2.5?3 0.21hfih kg 3 3.2.75 3.33351 5. "" .539 0.1.01.2" 3 60 h 7.2.91 0.5221572 6.03.5 2.2485 0.33555 75 5 5 .52 0.53233 5 .9233 2 .32" 0.33757 90 kuL2510szloaan..n 2.10:0.20xm flu.” mm: 2.2 IE'E:C£ZE?'1EITICH G? {3132323.3.’ 27.13.722.12? 422.3% "I” ’3’. 133 Ia . 17.10 m. s a 0.1332 9., . 6.595 80 “my-‘3 «(p #2:!- Izz 02.2.2.2 12-. "‘ 72:3 :9: 0.1 (II) 3.40....u2I1535 A; 1129 1’ II concentration (5J1) .' Pal! commmtion (mlurity) o 2.905 x 10 01010 t a time (22.13.1000) m1: I cm. 3.03 1.}: 0 2,1210: . 103 ram! 0 1 h.50 0.57979 6.235 2.807 0.1.2.39 15 2 1.63 0.56275 6.22.5 2.75.2 03* :32. 30 3 2.50 52170 5.122. 2.710 0.2.3291 1.5 b 14.95 0.573339 5.975 2.5-2.1. 0.1.2226 60 s 5.07 0.527229 5.852. 2.59 0.2.1330 73 6 5.21 0.51515 5.7229 . .2332; 0.2.0333. 90 w FL.- k . 1.3:. : 0.13 x 10"mm.“ . 1.91 :2 0.25 x mflm. _._‘..__‘ “v AL AM ...L. .- v—v—w ‘- WW. A Am 223:... LS 11333.2?(1‘3mfii (F 3333 wmmz.c*m P*BG.W'3 112 0.2.2233: 1:322:21023-3 AT 75 t 0.1 “ W1:- “3‘: ”:LZEL ‘3: 2“?"W2fmf’w : 3': 93:33 1° C 17.10 023. P I commtration 25/1) I. a 0.1332 J Pu II ammunition :mhritgr) 2.. 6.12.2. :Jiamleo mlnr 0 nun. (mm) 3:02:31. I an. 10: m r Pn:10' 10¢ 03x10! t 1 5.00 0.533203 5.927 3.12329 0-3339? 15 2 S .13 0.513237 5 .757 2 .379 0.37539 30 3 5 .Lo 0.50061 5 .533 2.295 0.35037 L3 2: 5.62 0.128326 5.353.; 2.23.? 0.33.57? 60 5 5.530 0.125215 5' .129 2 .113 0.32513 75 W“ “w :3: “:n r... ;x__ w... :::_,w=== .1 .1 k u 2.35 t 0.1:. :10" mm. - 3.96 t 0.23 x 10 m. _ _.._ ... .__ _.__._ m A...“ m.‘ fl WV... ‘32...- fiwfiwwvww wit 333$? Io . 17010 01%. ffimf‘!‘ Want. .5 11225.22 29 2...: CF 3334......{3’ In an: 133.] TT 211‘»: $un ..qu A? 55 t 0-1 ”F?” a, n “H “0:! iii»! m 12mm 2:: 6 w _ P I conrz..-ntz'ation gab/l) “-— .....— .-.-er--- was a. a 0 912 Pn '- 0021030th on wokrifiy) P, a 6.1.525 g./l . 2.3.3 3 10.802013: in . tine! (minutes) m1. 1 0:0. lo: 10/1 P anlo‘ . 103 anlo’ 0 I ' w “ MA .... w -.....Jfl. ii: A ““ “" =2: :2 1 1.20 0.60975 6.378 2.51.1 0.31228; 15 2 12.238 0.623156 6.2522 2A7? 0.39393 30 3 12.35 0.59651 6.2.?! ' .1253 0.39;?23 125 h 1‘ 0 £65 0.}: ~14 all 6 .113 2 0:46? 0.3 311.3 60 5' lug-’2 0.37735 6.62.5 2.380 0.375323 75: 6 L60 0.537623. 5.955: 2.31.8 0.37070 90 _._... A. w A.» ...4._.-. 1..— m l I k I’MtOMIIOJ mun. W L.— ....L w— A... A ...— yw— ww— L... A A. W A ....r.:t::*:*:: .2..- A A vw-u-v H ‘Twrw—wflw—w v—W.‘ Mlm:.wxwfimm“ fl vv—w TABLE 50 EECCJ’iPQ3ITIC‘fl CF 1313C. ’L’"L “1‘ ‘33"?1’1 P-'2KE.3 IN CA Lab“ T5F1A\hfladsr=3 AT 70 t 0010(1) Ww‘ - “:38 Io I 17.10 on. P a concentration (g ./l) s u 0.1:? ’n - mmtraticn (mm ..ty) P. - 6.115 3J1 . 2.1408 x 10" mom- 2. a an. (minntao) amplo I on. 103 10/: 2 ram)! 103 73110. t M. ......“ ##4##“...— w W w __.... W _ ———.__.—_._v. 1 24.654 0.555% 5.925 2.333 0.36791 15 2 1.80 0.55.7176 5 .772 2.272 0.35631 30 3 15.98 0.53577 5. (“2. 2.236 0.31.351 1.5 h 5.12 0.52373 5 .238 2.157 0.33335 60 S 5.30 0.523872 5.321 2.095 0.32118 75 6 5.1.8 0.1.9132 5.170 2.035 0.30355 90 ‘— w .7 fl“ *— k al.83go.09x10"m. - Lassogsxm“ ~wt—V ...fi— :1 w “w 7—7 *— ._7 WW 1'73 a “DWI fr ‘1th ...- 53302 $033133} Ci" 5:382:35? flit}: ”5.037310 ”C". 7'13 I}; Linn—JV o 1;». uh 3.1L: LIL:- 6’3»? la 2‘; 0.1 (II) _ ...; ~——-— ——“‘ 5;: 10.17.10 on. P o omwmtmtion (3J1) a. . 0.1912 P“ . emcmtmtion (:nomrity) Po . 5.51.3 ¢./1. II 2.179 x 10.: molar t 0 $1.33 (ramtoa) S'amplo I on. lo: 10/1 P mm! " log rune! t 1 5.20 0.51700 . 5.1408 2 .129 0.33318 15 2 5.112 0.139900 5.232) 2.055 5.31231 30 3 5.60 0.2.3131 5.071 1.995 0.30015 2.5 h 5.75 0.1.7253 15.943 1.93.6 0.259113 60 5 5 .93.: 0 .1592]. l; .5533 1.591 . ‘ 0 .27 5.39 75 6 6.12 0.1.2.525 5.553 1.838 ’ 0.25535 90 k- 1.90 i 0.09 x m‘m.“ - 3.17 t 0.12 x 10.5“.“ 1531 2.5235 52 DECOISP'CIl‘iITIOH OF BIS CYCLOI’F. “a ”33.21833. P330131... m 05.33% 733111532 10.12.. AT 73 t; 0.1 W v __ Mu ......LA A. _. “m _ ... .....mw ... 1” IO I- 17.10 on. P II concentrators éng) o 0 0.1912 Pa 0 concentration mohrity) Po II 5.!196 3J1 «- 2.1511 1 104110111- 1 :- tine (211mm) ———1—— ———- *1— “, . —v. 3.6.1. I on. 10: 16/1 2 2,.me 103 2510' t “A __ A 4—. M ~— w W‘— w ~— “ w “v WW ....vww —p— w—v— 1 5.10 0.50061 5.23? 2.062 0.31.29 15 2 5.61. 0.1.6172 5.039 1.932. 0.29735 30 3 5.92 0.16066 6.019 1.897 0.2730? 1.5 u 6.20 0.1.1.051 6.609 1.615 0.25860 60 s 6.50 0.1.2009 6.392. 1.730 0.23005 75 6 6.76 0.2.0305 14.216 1.660 0.22011 90 k - 2.9:. t 0.11 x 1t:1“‘mim."1 . 1.91 t 0.31 x m"»:.” WW “WW—.... m 15S mg 53 BECQEPOSIT‘IOEX w 01361010213010.1031}. P16111333 IE (36.18331 TESACEEJRILEE 111' 60 i 0.1 E j— 1* ¢+‘:_“-5{=5—-—' T“: ‘?w ..z‘-..‘ “1:;: A}: .353 In 0 131.51. on. P II concentration 23.)” o In 0.15102 Pu II concentration mkrity) P9 0 3.8;}? all I1.35 x 10 “W t I tin. (mun) 3.391. I on. log 1.]: r anm' 10; runs). t 1 11.35 0.522916 3.730 1.323 0.12155 60 2 11.70 0.1.3933 3 .1190 1.238 0.09272 1.20 3 11.83 0.1177168 3.1.06 1.2203 0.03287 1.30 h 5.20 .’ ’ ..543 3.17? 1.127 0.0.3.93 21.0 5 5.57 0.1.2305 3.020 1.071 0.02979 sec ___ A _ ....-. ... k a 5.16 t 0.13 a: 104m.“ 0 1.03 t 0.12 1: 1.0.5300. A ._‘... ____‘ ... A- Ahab-... _.__- __‘._ __.A_ .4... '— W — 155 2636.6: "2. "EITIGN 0F 31.)???» wfiTfim 3.011%. cm? 01:13:21 1 '1': (”TWE" 11' 70 + 0.1 (I) 1., I- 111.82: P I montmtion (g. /1) o :- 0.1002 Pa 0 concentration (0010:1129) P, I 11.060 ¢./1- 1.1150 x 10'. 11010.1- 0“ :- 1.10: (minutes) _.._._ ...—L ‘— AA A. H ‘#____.A_.#_!_ 500010 I m. 103 10/1 2 2,,110' 10g an10’ 0 1 1.03 0.55612 3.96: 1.1.0: 0.11.629 15 2 1.13 0.61660 3.891 1.360 0.13960 30 3 1.30 0.92796 3.756 1.339 0.12626 15 1. 2.08 0.61015 3.639 1.290 0.11059 60 s 1.60 0.1.9067 3.5.. 1.261 + 0.10072 75 6 1.70 0.60933 3.1.90 1.238 0.09272 90 _“ ...—4 A “A .L A w v V‘— W—v—w —— 'w k . 1.76 t 0.10 2 10am.“ . 2.93 2 0.3 x 10"”066.“ “7‘ ‘ ___. A A A ““ L __ .... w “ “.... 157 ME 55 1:60 0200366106 02' 0.6.m0m1mcm “2:61:16. 16 (262302." 2321:0110 1:26 12 70 t 0.1 (11) WW Io I 1.11.30 on. P - wmwtmtion éng) :0 : Elwin '- 2.351 x 10'. mm in: mfimfi) 6.01.11 .y) 5039].. I on. 1o; 1.]: r 6,900! 10;; 1,1210" 0 1 5.10 0.16710 6.621 2.312 0.30399 15 2 5 .30 0 #1715 6.379 2.262 0.35009 30 3 5.06 0.1.3020 6.1953 2.197 0.30183 05 h 5.6:. 0.2.2015 5.990 2.126 0.32765 60 5 5.75 0.2.1176 5.57:. 2.083 0.31869 75 6 5.06 0.1.0353 5.75 2.01.1 0.30901. 90 k a 1.68 t 0.09 3 10am.“ I! 2.81 1! 0.15 x 10"”. W —_ WW ..w w w ‘— w nag 5T6 I‘”G"" QI'IT ON C? BIS-3’3 YCILC". 2-61:. ‘A’ :‘TEL Pfi'i‘flfllffi ‘ m LA;);LJ 3.31"" ‘1»..- 83“! n-jrmn 44L..u..-'.1 AI 75 '3: 0.1 133 Io '2 10.53 on. r . (:0. animation a . 0.1.3 02 P . c021 ncmtratian mhrity) Po - 11.190 g./1-1.Lss x 10" nom- t a t (mag) 31mph I en. lo; 2J1 :2 anlo' 1.03 anm' t 1 3.89 0.57108 11.075 1.2.05 0. 5987 15 2 11.12 0.51.653 3.598 1.332 0.11.051 3o 3 11.21 0.53715: 3.331 1.3339 0. 3322 2.3 L 11.05 0.3“ 07 3.560 1.2328 0.11.327 60 5 11.60 0 .1336? 3.557 1.251 0.10072 75 6 11.83 0.1.7703 3.0025 1.203 0.03207 90 W Vv v V‘— k - 2.21:0.nme-m. A‘fl .3 . 3.78 1 0918 x 10.3.“. ___— ...- Figure 11. Plot of log k versus l/T for the Decomposition l of Bis cy010pr0panefom1yl Peroxide. 1.11” 1.0 P.- 0 2-2 ~— H H 3.". ff 0.0 "’ 0.7 ""— o.6 L— .0291— C’ 9 2 .89 2 .92 2.95 2.98 ‘~ 1.30 Figure 12. Plot of log k versus 1/'r for the. ercmposition of Biacyclobutanefomyl Peroxide. 1.2“- Leg (1: x 105) 1.0?"— 0.9 r— J 2.90 2.92 2.9L. 2.76 2.98 1/Tx 103 X 10‘“) Log \K 0.8 0.675 0-55 0.1.25 0.3 0.175 Figure 15. Plot of log k versus l/T for the Decomposition of Biscyclopentanefomyl Peroxide. — 3 .07 3.12 l/T x 1& 3 .17 1‘31 Log {K x 10*) }\ 122 Figure 1h. Plot of log k versus l/T for the Decomposition of Biscyolohexanerormyl Peroxide. 1.0 0.875 0075 0.125 0.50 0'375 —— I l L J l I 3.15 3.17 3 .19 3.21 3.23 3.25 1/1' x 103 1.25 1.20 1.15 1.10 1.00 0.95 0.90 \- - x _- '\ \, . 1 -. f .. figure 1%. Plot oi lo; 5 qubUS l/T for th: ’ “ ... . «a 1 ..$. ~,- 3" . V' ‘ -“'- v o. DlSC‘LLOchocuciUThyl fieroiiuc. 3-155 J6 3.18 I 3.205 l/T x 105 erorrosition l 3.23 L 3.265 143 L03; (k X 105) 2.07 1.97 1.77 1067 1.57 1.117 1.37 Figgre 1:3. Plot of 10;; k versus 1/‘1‘ for he Decomposition of Discj'c]oprozsneacetyl Peroxide. 1,4311 3.365 3.55 I 3 .035 l/T x 103 Figure 17. Plot of leg k versus 1/1‘ for the Decomposition of Bisq'clobutaneacetyl Peroxide. 0.65 " 0.525 " 6? 53 K 0.1.0 1- ii .5 O ...] 0.275 1' 0.150 — . 1 1 1 1 2.91 2.96 l/T x 103 F gure 19. Plot of log k versus l/T for the Decompositiun ' 1 .‘ 4‘ $ 0 0.675— 055 "' E? O H K x v 0.1.25 1- :5 O ..J 0.30 '- 0.175 "" Biscyclopentsneacetyl Peroxide. 2.91 2.96 l/T x 105 Lo.r;( k x 105') 12’37 Figure 19. Plot of log k versus l/T for the Decomposition of Biscyclohexaneacetji Peroxide. 0.575 L- O 0.50 " 0.375 .- o.25 "" 0.125 L— L l 1 1 l 2.93 2 .98 l/T x 103 168 .ou 9:03 am nopmanH Mongouaoaoaomfim mo 52.3.00 has magnum H 93.83. 5“ namcmaozw; ON 0: 0m om OH 98.8.; 5. 23003.53 . .oeflaumm Hgowmcdpznoaohomflm no 6.5."?QO 00.22de m d :8 0.3m?" HA fl _ A . a _ r2}. 170 .mefinoumm Hafiomocmfiomoaohomfim H0 ”.200on egaaH .NN geam 0:98 a: sun newscaobfl.» _ 4n m.” .3 0H m m N. w m1 4 m w _ 1 1 _ _ 4 J _ _ _ _ 1 ON 1 8 .. .... ow ->--- ....-A.‘ --n—fla— ...-- 171 .mefixouom Hénomocmxmnoaomomflm ...8 1.5.30QO voamth .mm magma 000.802 5 51.02.3020: fl ma NH 2 S m _ _ 1 _ _ .6 1 .1 m .. m . 00.... 172 m _ _ . 17.1.1an I 'Il.--‘ II- 9.1 .mnfiaogmm H “.....Momosmdmmzoao Umflm .3 15000on vmumpwcH mcopofig .3.” npmsoawecwc. .3 OH m #3- w ‘1 41 Ill" .Jm mhdmfim .. 111.1‘ ..I. .-.]! «I. J q -—1N’\ OOH 173 NH U A— _ p M O M_ U .- p m:,AuH2 2w AwMCon>mx m 4. OH m Va A: w .m&. 05~wfim _ w _ A _ W ‘— A ”H o: Om OOH 17h .wvfixdpmm Hhkummcmpsnoaohundm Mo azhpommm umuMAHcH .mm mhdwwh 98.8.3 5” 3933953 9 on m m .5 m m 4 m _ 4 _ _ q _ A _ 4 IlLow IL. ow OOH 11019911118qu '1an Jed .mnflxogoa thoomocwaCmaoaonomHm mo Suppomam wmnzpwaH .NN mpzmflh macho“; Cfl newcoam>w3 175 +3 2 [la - m 5 m m a m a fi _ A 14 _ _ fl J 18 Jo: * n18 10$ 1. 8H uotsstmsueam queo Jed 174 .mvflxcpom “Swampfiflfiozoaoufimfim mo nmnppocaw nopmffiLH . mm 8% E mcopofla cw :pmccamxfiz fl 2 S 0H m w w 4 m m . 1 A O A A _ _ _ IL ON ‘ \ :16: L8 .1 ow OOH .-_...~_- Ha OH -.----..:_1 _.1; . mpwafiepgg oqwaobmoao no 9590 as aw Spwnmampmg m m N. ._ -. -.. .. I A. I '1‘! |-.-lil"i. AI.III1:lO-I Hnmopmoao .6 mo 5.309?” amps-“.2; .mm mhsmflm 11-. .- --.m -,1-l|1.fl O 40 w m . :4 a- ...—... 7" , A‘Vfl— IDA *F.‘ fl‘rI\'I‘..- 9 - -11-? .11. - 11 L02 78 OH .mpgmommcwaopQOHomo Hmz-maoH-Bopmoflmo mo 52.30QO wand-QCH com opzmHm mcopoHa :H camcmHopws m m n w b m m _ m _ fl 4 _ H _ 2 d N ll OOH 179 .HocmgpmocdmouQOHomo mo 9940QO Fig-EH .Hm 93mg 98.8w- 2 CH :fi~con>m...» fl 3 «H S S m w - m m 4 m d _ _ _ 4 4 _ _ _ 4 4 l ON 04 00 Ow OOH 180 .ov-EBVHmvmomgmgoanOHomo mo Era-«comm “yew-H24” weep-0H: :H :fiEon>m& m m b P 4H .mm 2% E m a m 4 4 4 4 4 4 J OOH UOISS‘UILSUBJL 11:99 Jed 181 ”72} OH H .wUHdoH 630.3036 mo 54u-tmqw fiend-HE; .mm m-Smfim 940.4on CH nfiEmHm>mB m 4 m A 4 m 4 4 4 H 4 glow 182 eecoHEpmHmmonQOHohuHothH mo napomam neg-HGH 1.4m 925434 98."on :H 44.553453 on m m k. f m 4 m 1 w fig H fi H 4 H H 4 4 L 83 HH Qfimucg. :- 4 .,-.o-...H-..n-Elth ”-40:33? Bag-mam. HE‘S mo 454,303.43 . . wccpo H44 CH grim-H929» t; «4) _‘S “Ell OH O H 4. H H 4U“ fl _J ON 04 Ow OOH no :83 123111211, quao .Iad MH 4 .4 H . 4Q memd mm 0.2%. amoaQOHd-GHQImam .Evm mo 445.30QO we .09 4Com .r m w «20.334 5” 5803452 4. w m .4“ _ 3 .4 . 4w 4 4 4 H 4 4 4 44 i a .4 om [YO-J [8 [Ow 185' . Honoo H4 HAHHQHESQOHohv Hanna n no gunman @23th .nm 0.33m £8.82. :4” gngflI 186 oHIHocmaonQH-thmgohuElfin Ho 83.38am 68$de .wm 93mg 98.843 pH 5.943963 3 m 44 4- m. m 4 m 4 H J fl - C4602 OH .mpm-LOHQOMQHEOAROHCNUHRA‘H.m H.945 ,Ho _Epomum 45.5.5451. .mm mpg-him machoH .4 EH ngmHm>dz ...4 m 4. N\ N H 4 4 w fi ON 04 Om OOH FFCi 3 4:? MAY 3055. IUG 5 ’61 APR 25 ’52 CHEMISTRY LIBRARY