MMSMMWMW%WWW @Afi? AN M‘ESYmWié 9F M CMWYL WTBON BAND (if A ms 3? W W WWII: PM? H \MEY‘A A games 35 N-W3 1mm 54? 112.9 m sé HR. 9‘ RECW £1533 QWW mm .3 Regan W57 RAICHIGAN STATE UNIVERSITY U‘ AGRICULTURE AND APPLIED SCIENCE DEPARTMENT OF CHEMISTRY EAST LANSING, MICHIGAN - F I, I E" f? 2‘ 7’. Y E DAR [75.1" :53th 0 J UIL'LVC‘L‘iny MICHIGAN STATE UNIVERSITY OF AGRICULTURE Arm A:‘P-._III.D SCIENCE DEPARTME .T OF CHEMISTRY EAST LANSING, MICHIGAN A23 ENZSTIGATION OF THE 14011:. 211mm REACTION PART I All IIWESTIGATION OF THE “330m ABSCRPTION BLED OF A amiss O? was ARI) l-BRG‘MTIDEB PART II DECWWITIOK 01" AND BRWATIOI WITH A 8mm 0! Nv-BRW By John 1'. Ram ATHEIS Submitted to tho School for Advanced Gram“- Shun“ of Michigan State University of Agriculturo Ind Applied 801m. in partial fulfillment of thc "gum for the degree or DOCTOR OF PHEOSOPHI Baum of 0119mm 1957 AWNGHLEDGEEM Thenthuflmeete «pruni- mud.“ Pretueor Robert D. Sonnets tar hie direction and mom-em througimzt the wee or this work. Appreontion 10 also extended to Dr. Theodore Brown and Profuaor Jame. Steuben m mum; mummomwormmmmdum- violet data and to the Michigan Chaise]. Gm for W W of thie to -. Th1. work m not he" been ponible Imam. the new nuance. or the nthar'e lute. In. W VITA John 1". Began Candidate for the Depee of Doctor of Philoeophy moa- Subjeet: Organic Chemistry m Subject“ Inca-gum: and Analytical Chemistry Biogephioel Dates Date of Birth: Become:- 22, 19253 Boston, Haeeeohueotte ”more John J. Regan Bother: Hora homey Regan Education: at. Marga-eve Elementary school 1931-1939 Boeton Latin High School 1939-1913 Boeton College 19h6-1950 B. 8. Meta Michigan: Stete 1111:157th 1930 Merino” {Index-mu W Baotou College ery to m 1950 Gndmte Aeeietent Michigen Stete University, 8m, 1950 to June, 1952 Rommel: Fellow, mchigan State adversity, October 1952 to September 1955 Putnam “Motions: American Chemical Society The Society of Sim n The Reeeerch Society of America the Society or Sign Pi Sigma 111 nmnuammnmamw PM! Al mmflou W $333 exam WI“ m (U l 8%133 w M32353 w momma 1'53! 11 ummwmmmm Aenmwlmmou W “fem mmummmmmamuemormn ‘ - e1 momma-em. moms? NET 3 The infrared meotre of e nation of exams: and gamma» were studies: with particular enzyme on the carbonyl m. thie- m m oormw out to (Tetomim 1: 80-3-10 progorty revealed by the meow mold be related to the 7min; behavior of the fiflommidee ee bmtiw egente. The Maid had me chem e-inco any electrical]. affoota im’laoming the nature of tho mtrogm broodne bond the to variation! in the etmture or fi-bg'omwidee mid to tram fitted t’n'ougm the carboxvl your: or such cowmoxie. The following W we studied: motezfixie, chlorowetmlcie, éiohlomooetwdde, triohloroeootemde , “homemade, fommiée, Wmstaflée, propioowsawe, phwlecm'aide, Woo, fi-brorao mono, 61 on: Moiflorowotomoel. Carbon tetrachloride and chloroform we need a the commits. The absolute int-oyster: eimorp‘aon ammo. peek treqnmoiee “womeof‘memmmflmmlhudm Med. Brownian“ mummtedfmw “mathemuonbmd curfew oomhavethetme WV 73139. enmemmpmwmmmmmu Wt? mmmmmrmmummmmum- WW» ammo; ems etfiwmoto’omo. In those ones. otm offset. b83169! the alootz-mmuviv of the 111331.1sz W m mt. ‘8‘in 11m mutiansldp m ulna mzibitazfi by the We.“ Met? . '2'?» “We: have wmmwly the was W1 peak trsquamy but a mm}: 03113133? intensity than their wmmmm W aid-Lian. The Mint: infirmity “12:33 or the cyborg). haul, in the mid“ and mm ”Math-as, cam foam: $3 m higher mt: that peak anaemia law in «315:9me than in W hireshlorida. Tbs diammstry 1;: the carbom'}. ubmrytion curve: at eons of the was. magenta: that far them: sumac mm than an. ram of the normal vibration for the carbonyl mp mu. mu m attributed hfinmodfiahfly groupsnnthoomalmntothn mm W causing Q Ma hfizéhitim to rotation at thin alpha mmmgmmmruwunmuuwwumumnpm m filth wt to the plum 9! W8 0! the and. m. Tamas was humane-ti in. the (30.1% by Emma new. ($1 and triohlomcatamide ma. bromine at two mum, m” and 80°C., using «eminent cammtratiom of all the “new“ in we}: mum. Thu lawman *m prepmed by adéing Momma to a m: of tho Md. and silver add. in We“: acid. “tap“ to prep." WM“, Edbramothommtmma and namzwmma by mu method In mum and led to ammonium of the 3:21:33. v1 rho “tons or um: um and ring bromination m follow by twisting the reaction precincts mm mam-ting the ml”. 1 mural mama! atWWWumoftnommcmflmmdmtha W at 80°C. which ms allows to go to mutton. A material balance of 85 to 99 pm- «at u attained in the mum at ”.3. shiah var. dim-:1 ‘59 run rm- meaty-tour hours and warn 1mm”. The extent of 83.ch chain watfimn at the We tmntm'n L0 and 80°C. {Emmanuel in we ramming ordar, lax-wig» a» K-brmomé Mauricio s» fi-brméicflmacmm :5 Macmazlmmemmo. In the manor!!! at ne’er” which man mamlm. tree broaina III. “0th in each can. Am tho “mar-sides tha flwmmobrialdorawmsfio shouted tin {m rate of reaction and the fl-bramommcmormufido the W rate of reaction. m ”lulu obuima 1n the metal inc? photochmicel (face-mum at the ”Misfit!” van «triad, out: war. not emletely reprodnublo. m, chhlmwetaz-dde theme! tho tube-1s rat: at ammonium and mmwlmncwo thc W ah. the W found during the (Emorqmaititm m {m M b. Wad with can: own 0mm! formed «aux-13¢ tbs «mum. mo dampen ufimrmummnudatmimdtohatowu inn-taro. A melanin of humiliation with “maid“ involving the W MWQ dislocation “the nitrome “unauthmnonoimmd&bmmm~w 711 ”—43.2.- :~;x.* ;'=‘ ALMI‘Z‘ nu- <‘W "xi; f-mém.aw Vt“ . based on the correlation of the infmod, daeompouition Ami bromi- mfim an. “WM! 31% a , N-cibmmdizw'wlhflmtoin m moved to met with cyclohezme in refluxing chloroform and cumin “mm“. In chloroform only 1.2 dibromcynlohm In! tainted». In carbon tetrachlorida 3-brwouyclaimam m 1,2 mmaocyulnrmm we mum. Tim fi-brwwfiwcinifldda awn 63 per amt $111116 minimum: mfl c. malls: mm a: tux-y mime am 3, 545331-93»- dim? ’lhydentoin this}: 533210 55' par amt {Dyna mamfiw. Putnam ammo tatrabroméa, may“ In prep-rod and aloud to react with cyclohaxm. A can amt of anylio mum «curred, but min): 1.2 dibmmyclohm m obtains}. Phosphat- uitrflio bromiéo m pmpnrod ma mm to react with cyclohmrano. Allylia Maximum or brand» additian did M 0m: TABLE OF CONTENTS has an! I All INVESTIMTIOH 0? THE CARBONE. ABSORPTION BAND 0!‘ I am 0? mm All!) IWM IHTflqpucrloxI...OOOOOOOOOOCOO.DOOCCIOO0.0.0.0....0....COCOIOOOO’ HISTORICALOO0.0COOOOOO0.0.00......OOOGOOOOOOOIOOOCOODGODG‘IOOI. DISCUSSIO'COOCOOOOOOIOOO.I0.00.0000...9......OOOOCOOOCOOOOOOOO. EXPERIHEHT‘L...OOOOCCOOOOOOICII.O'COOQOOCOCIO.IO000......0000D. “Magoo-0000.00000-000000...oooooooohoopoo-ouooocoon mm...90000900000000.0000.no...0000.00.00.00...coo.co 'I‘WCtifin Of PWhOMdOooooooooooaooooconQQDOOo-oco Pmnon O: PMiMCOot000ooroooootoooc¢§ooooooooo. Preparation 0: W".°.u3nid.0000000OOIOOOOOOOCOOOOOO. PfW‘ti-Gfl 0f EthflmDMdOOOOQOOOOOOOOOOOQGOOOCOQOOOIO Prapmtion Of Chlomwmd.00000000.00.00.00.000.0.0... Preparation 0: nichhmo.tmd.0000900.0.0.000.0.0.00.00. kporimontul Wtimcoooocooouooooooocooooooooocooocoo. W 0: Ohm About!“ thIOOQGOQOOCOOQQOOOoooo SUMMARIOOCIOIC0.00.00.000.00...OOOIOOOCOOI...OOGOOOOCOOOOU.OOOO PART II DECOR-{POSITION 0!" AND BROMIXATION ma A 83.3133 0! H-BRQ‘IOAMIDES IXTBODUCTIOHOOOOQOOOOOOOOOOOOIOOOOCO‘OOOOCO...O...00.......0... HISTORICALOOIOOOOCOQ...0.0...COODOOIOOQCCOUCOOOOOOO0.000COGOOOO DISCUSSIouOOOOO00.0.00...C0.0...0...0.00UOOOOCIOCOOOOCOOOOO0.0. mmmmnoQQOOIo-ooooocooooooooocoouoooo-oooooooooonooooooonoo Reagan. w Ammooooooo000.000.00-ocooooooooocooonoo PWItifln 0f Phospbonimno WCocoooooocoooooocoooo Prapnration 0f ‘11-’95“ amid.000000000000OOOOOOOOOOOOOO. 11: h? 8h 814 814 85 1mg OF CONTENTS . Continued Page Preparation of a nitrogen Sulfide Bronido................. auction of Phosphanitrilie Bromide with Cyclohucm . . . . . . Reaction of Nitrogen Sulfide Totrobronddo with Cyclohum auction of N-Brommocinimido with Cyclohueno. . . . . . . . . . . Reaction of H,N' oDibz-omodimothylhydmtoin with Gyclohozono‘ PrOpu'ltion 0t "WMHOMMd00300000000out...o fropm‘ttion of N'BNMOthMdaoooooooooooooo00-00 Preparation of N’BmwtriohlomoemeOQOOImo000.0000000 Attempt“ Papa-ulna or RoBromocthoxyuMdouuuu... 86 87 89 90 92 9h 96 97 99 Attempted Propunuon of l-aromphwhoamido...uuun 100 “M1031 30.8331“.coo-ooo-ooon0.000000...0.00.00.00.00o. 10]. W10“ Pmmuooouoooooooooocoooooonooo0.0.0.000... 101 auction or N-Bronotrichlomacounidc with Tainan-u... . .. 11]. Reaction of N-Bromodichloroaootmidc with Tolumo......... 111: auction of li-Bronommchloroaoomido with 20111050.“..u 117 auction of Brazil“ With T0111“...oooococooo-oooooooooooo 120 Mowodtion RucumonoooooooooGout-00000000000000.0000 123 WWI.0.00.00.00.003000000000......QOIOOOOOOOQOQOOIOOQCOOOOO. 13h “MATURE OHEDOOOUOIOIOOOCO.IOOOOOOOOOQOOOO§OOOOOOOOOOOOO000’ n5 MWOOIOOCOOOOOOOOO‘QOOOOOOIDQOOOQIOOOCOOOOOOOOCOOOOOOOOO... mo .I. !u TABLE I II III XIII XIV LIST OF IAELES Page Voriatim in ”money md Apparent Intensity in Chan.- ing From Carbon Totmhlorido to Chloroforn u Solvent-u 18 InfrIer.‘b.°rpt10n.Dlt‘ for Formlmido....o.........o.... hl Appu-m Integrated Absorption Intmitiu for Sam ‘flidfil and Thai: H‘BTDEO DOIIVItiVCUC-ooooconcoct.to...co h3 m. Integrated absorption Intuition for some Amid” and Their N‘BPOND DETtV‘tXVCiooooo000.0000.coococoon...co hh Amount of Sid. Chain m8 Ring demtion of Tolum vith ‘h. H-BronocmidOI Ct no and 80 Coco-000000coco-000.000.. 6O Remit. of the mutation of Toluene with Bromino and ‘h. H-flronocmidol I3 80 COOOOOOOCOOOOOOOOOO0.00000010.... 71 Result! of tho Bromimtaon of Tainan. with Bruin. tad tn. H-Eromoamidos I‘ he coooooooooooooccoqoooooouoooccoco 72 Result! Obtained by Park on the Broodmtion of blow 'dth ‘h. K‘BTOIDImidOCoooooooo00.0.0.0...ocoo-0.0000000to 77 Bonita of o mug-um or Tainan with the l-Broaoo IlldOI .3 ho .nd 80 OOOOOCOIOOOOCOOCIIO00.00.000.000.COO 77 8m 01‘ the Minot”. Botswana!) of Dwain. in a W Gad-tin; of Donal Brando, 0 3nd pom-onu- iolucm, Monies-mound.“ we! Bani “manna..." 109 Longthotflnoorxrndimontorthommitionot ‘h. fl-BromotrichloronootUILdO............................ 130 How Extinction Miami. for tho Durham. Band of Son. “*Brfilfl.lid.. tn Cafbon‘foirlohlorido...o...o.o..... 133 Infrlrod.lhoorptian 53“ for LQO‘CflidCooooto0000.00.00.00 1h° Infrared Abnorption Data for Propionmddo................ 11:1 Infrared Abnorption Dots for Macadam. in GhlflrOfbrloooooooootooooooooooooooooootooonooooo-oooooooo 1h: memm.0om {All Page m Infrared Absorption Data for Ethoxyacetaude in Carbon ’ Tetranhlorid .OOOOCOOOOOOO00.0.00...UOOOOOOOOOOOIOIOOOOOO. 11‘} XVII In!!!“ Abfin'puon a“ far cmcm.eeeeeeeeeoeee 11th XVIII Infrared Abacrption Data for Dichloroacotanide in MNOHOCUOOOOOOIOIOOI.00....IOOUOOOOOOOOOOOOOOOO0.... ms XII Inna-ed About-pun Data for Diehioroaeetaadde in Carbon Tetraomori d.IOOOI.OIC.OOI...0.00....OOOOOOOODOOOODOOOOI. m6 :1 Infrared Absorption Data tor Triohloroaoetanixieuuuun 1h? III Infrared Abeorption Data for Trimoroaoetande.......... 1&8 XIII Infrared Abeorption Data for Maude...............'.u. 1h? XXIII Infrared Absorption Data for Phavlaoetanide............. 150 Infrared Abeorption Data for :3 3: “‘ “ “‘ . 151 Infrared Abeorption Data for N-Bronodiohloroaeetanide... . I52 555 Infrared Abacrption Data for N-Broaotriohloroacetanide... 153 LIST OF FIGURES FIGURE I II III d VII 5 55235582“ XVIII E Effectire Electronegetivity rerun: Carbonyl Peak Frequency {01' C SW10. Of Mdueeeeeeeeeeeeeeeeeeeeeeeea True Absolute Intendty Verena Carbonyl Peak Frequency for I Berle! Of mneeeeeeeeeeeeeeeeeeeeeeeeeeeeeeaeeee Carbonyl Abnorptian Band‘for Aoetuude..nu..n...uu.. Carbonyl Absorption Band for Chloroaootanide............. Caz-bowl Abeorption Band for Dionloroacetanide...u...... Carbonyl Abnorption Band for Triohloroaoetamide..uu.u. Carbonyl Lbaorption Band for Ethomoetanide..uunuu. Carbonyl Absorption Band for Fernando...uu..uunuu carhonyl Absorption Band for friflaoroaoetande...uu.u Carbonyl Abeorption Band for Propionanide......uuuuu carbonyl Abeorption Band for We................... Carbonyl Abaorption Band for Immanuel-idea Carbonyl. Abaorptdon Band for l-nBromdiohloroao etanide . . . . Carbonyl Abeorption Band for l-Bromotriahloroaoetamide... Carbonyl Abeorption Band for Phewhcetanide..u.u...... Optical Duty of the Bromine Aheorption Band rem The of Irradiation Of 'WflWOWdCeeeeeeeee Meal Batty of the Bromine Abaorption Band Verena fine of l-Bronotriehloreaoetnide Datamation with and ‘M‘ 14d“ mm0eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee Optieal beauty Verne Communion of Brenna at Page 12 20 21 22 23 224 _ as 25 27 28 29 30 31 32 65 66 Different HIV. Lumeeeeeeeeeeeeeeeeeeeeeeeeeeeeaeeeeee 128 Optical Mt: "rm We Length for the Deooapoaition d l-Bronotuohloreeom during Varying Period! of mumeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee 129 1111 PART I AM INVESTIGATIOH OF THE CARBON LBSCRPTIOH BAND 0? A SERIES OF ”(IDES BID WWDES MODUCTION IM'ROHICTION 'rhe Hohl Ziegler reaction involvea the reaction of an N-broeoc amide or inadeuith anuneaturatedcmwonndhavinganethylor methylene groupadjaoenttethedcublebonduintoluweorcyclo- benzene to introduce a bromine atom in the allylic poeition. In motion with making a comparieon cf the Mounting propertiee of WW» iteeemcdedvieableto etudytheiretreoturee and the Motor“ of the emcee from which thw were derived for the mace of detox-mung how variation in the W attached to the carbonyl group would effect both the brominating propertiee and wrered epeotra, particularly the carbonyl band, of mob commode. The l-broaouddee and unidee are capable of allylio breainaticn ”vellumlearhrodmtien. Thieeeeeetabliehedbytheeork of Dam-Roi (1) who studied the action of ll-bronoeuocininide on a wide Variety of bonanza and whthalene derivativee, notably ethm. The dual bronimting character of l-bronoiddee baa more recently been mud in thiOphene (2) and ite m1 derivativee (3) when both Mechanandmclurbmmtionhavebmoblmed. actuation- ef the HM“ and inidee and the mechanin of the reaction are Watlenguxiatheeempartofthie theeie. Aeenaidin an attwt to elucidate the mechanism of the Hohl Ziegler reaction theetfecteofvariationeintheetrectureofthehrominatingagem on the reaction were etudied. Thilmapproachedbyaei'ndycf theinfraredabeorption of acne typical Hchl Ziegler allylic mounting agenta and their parent anidee aith particular reference to the arterial group. The parent amidee we included in the inveetigation ac that if a correlation «dated beta-en the infrared aheorption epeotra or the i-brcmoamidee and their mounting propertiee, and thie correlation eae exhibited alee by the mom amides), it mid to pceeible me the infrared abecrpticn epectra of the amidee to predict the brominating propertiee of other H-brcnoanide. It III expected that any electrical affecte influencing the nature of the nitrogen halogen bond due to variation in the atmcture of either amidee cr inidce weld he tranexfitted tin-cugh the carbcrvl group of each manna. Time, the relative tendmciee of the nitrogen breedne bond of the Mronoanidee or iaidee to undergo hono— lytic or hetmlatic dimciaticn ehculd be indicated in variaticne «Winfraredabecrpticnhusdcfthecarbonylminmchcomnde. Farther, ithehcpedthateomecorrelaticncculdbefonndbetueen venetian! in the infrared abeerption cf the carbonyl group and the humiliating activity of the allylio breninaticn agente. Thee, thil partefthetheeiedealeaithaetudyoftheinfraredabecrpticn epeetre, particularly the earhcmrl hand, of acne “idea and their hire-Io derivativee. 'l'he abeolate integrated abeorptica inteneitiee, peakfregeaoieeandthemapeoftheaheorptioneurvecftheearbcw‘l ham eere etadied. HISTORICAL HISTORICAL The intensity of an inhared abacrpticn band ie proportional to the eqnare of the oscillating dipole moment for that vibration of the molecule giving rice to the abecrpticn hand (h). The dipole mutant change (h) is pron by the euqyreeeion, (en/co), where a in the molecular dipole moment and Q in the norm]. coordinate dmribing the particular vibration. The integrated intcneity for a band he: been ohm to be proportional to (cu/co) (ash-1th reepect to the meal coordinate of the vibration. The correlation of the latter quantity with knoen or calculable molecular propertiee hoe mt ae yet proton very eatiefactcry. Barrow (h) demonetrated the relationahip m the reeonence «cry and the inteneitiee of the eawcnyl maheoryticntcravariebrcf compoundeuth mhapouppreeent. Half and Liddel (5,6) diamond the nitrogm-tmirogm, oxygen- hwdrcgenand carbon-m'drogenbondahecrptione feravarietyefccn- pounce andtheaannerinehich thepoeiticn, ehapeand inteneity of theee ahecrpticne are dependent on the neigzbcring groepe attached to not: bonda. The relationehip bctm the electronegativitiee of eddacut ntetiteente and the etc-etching frequency of the carbcwl group ofleetere, acid halidee and aldehwdee eae ehmin by Keg-rice (7). Therehevebeennenercuectherinetanceerepertedinthe literature dealing Iith integrated intemity memento in infrared ehecrptina We each ae We each (8) with the ketoeteroide and the inveetigefione of Francis on the carbon-hydrogen bond in aliphatic hydrocarbon (9) and hatches (10). Ho eyetmtic instigation of the integrated inteneitiee of the carbonyl group of amides or H-bronoeniaee eppeare in the literature. In feet net of the epeotreecOpie work carried out on the amide snap hae been with proteins and other biologically important eon- pounde. Comiderebly leee data are available on the epectra of eimpler «idea. Beehuell, Rodehueh and Roy (11) have concmcted a thorenQ epoctroecopie etedy of. amide aeeoocietion in the near infrared ream. Recently mm amidee end Witnted amidee have heal extensively mono in the 6 nicron region by Lenoreant (12,13,110. Hie reunite have rather definitely eetehliehed the kete torn ae being pram in the eolid etete. Lenormnt (15) hee aleo confirmed the prwicee aeeigment of hence in the 3 micron region to the nitrogen- hydrogen nmdamental vibration by substituting deuterium for the hydrogen! on the mtrogm atom and chewing a eoneequent ehii't in theee bende to around i; nicrone. Richard- and Mean (16) have conducted the met detailed epectroeoopie find: of the amidee thee far and have been able to interpret their data tree a eoneideration or the hate fore and ite menace dipole: etrncture. Beau and Barker (1?) have conducted an X-rey anally-lie of the cryetal etrnehre ofacetuideandhave round it toendetenlyintheketo fore. They eleeeonclededthetthemlecnleueplanarvithreepecttom carbon, nitewogenandeaygmatoneandthettheaolecnleeereeencieted in ring poly-Ice through nitrogur-hydrom-mgen bridgee. Recently Perk, Lechor and Tompkin (18) investigated the nitrogen hydrogen fundamental bend, 2.93 microns, or a eeriee of alpha halogen N-bronoamidee and related the molar extinction coefficimt to the broninating activity of the nitrogen bromine hem. DISC SSIUH DISCUSS 1011 A For moleculoa of the type, )C- G, the abeorption bend aeeooieted B with the carborwl etrctching ie the result of a normal vibration involving e carbon oxygen etretching and come combination of etretching and bombing at the 0-41 and 0-3 bonnie (30). The actual tom which the vibration aeaumee for a particular molecule ie dependent on the mean or the atone or groupe A and B, and on the force conetante for the bond! C-A and 6-3. In my interpretation or frequency and intmeity ohangee reeelting from etmoturel modification two factore met be considered. First, the form of the norml vibration and any changee in it occaeioned by etmotoral variations, and secondly, electron dietribution in the file. eele and the way in which it ie effected by changing the ecbetituente. ‘l‘heee teo factore are not independent, eince the tern of the nornl vibration ie depmdent on the force conetente of the bonde mioh in turn are determined by the electron dietribution. The frequency of a vibration ie determined by the noun or the vibrating atomic epeoiee and by the force comtante for the We involved in each a vibration. In quinonu where the action can be eeeumed to be all carbon mean etretohing, the carbonyl Its-etching frequency ie linearly related to the calculated carbonyl bond order (31). For a «rice of ring mbetitnted acetophenonee, where a nee effect due to ring abetitution ie negligible, there ie a nearly linear relationehip between the Hemmtt 0 values for mhetituente and the fmwmqefwemwwmbmdfifi.memeflmamnflcmmen my be inferred that the frequency of the carbcrnrl stretching vibra- tion in a eeriee of commode increases with increaeing electron deneity in the carbonyl bond in the ground state of the molecule. Bhifte in carbonyl frequency in terms of the electronic etruoturee involved have more recently been considered (33). For the carbonyl group in amidee where the carbonyl group is conjugated with an electron donor group the moat imortent resonating forms are considered to be , in addition to the ionic fern inherent in the carbonyl group itself, of the following typee 1“ ‘t\} - 0-0 and c-o 3’ a3’ (a) (b) Time, it ie to be expected that etretching of the carbonyl bond will lead to an electronic etructure of the molecule with a larger contribution from the charge separated canonical form (1:) than in the molecule with equilibriun bond lengthe. Thie increeee in contribution from the ionic form will depend upon the availability of ouch a charge separated electronic configuration. Thie effect would reenlt in amidee having lower frequenciee than eetere and other mbetancee in which there ie not each an availability of a charge eepmted canonical fern. Recently xcgcriee (7) concentrated a linear relationship beMen the effective electronegativitiee of adjacent abetitnente an: the .. .. V __. _ . _ > .~ vr_ ‘uwv‘ vy—..,‘,‘.—.-w‘:- _,~ ‘ ~ ._ H . «I’m mung My of tho cam-bow}. m. This ”hump m dam-tram for Wu, «1d halides and Iota-I. Intimolulhomupm otthomddo cu‘bowltromim "rm thn “thou" dwtromptidtiu for than aide. in Tabla III dam «tooth. dutrmmttduu In!" either km or could be mmmwuuorupuum. mwgmmm R match. Rom. “meta-amused. Thanh” $1011er calculator! me than for We and emanation-1d. 1.1: inch flaunmwthnn-mutu. mmmmm up. I m; a, «mac; b, gum-opium; 3, Wow.) 1, Wmmdu o, tarmac; 1', diam-mama» g, Memora- Woynflh,de. mmwngmwnmnummump “mommmmmmwummw «noun thnu of thc mm m. Th. than ”gunman-aide, W0, “W0. vmmnwwmuummummmuw 1wm,1.n,wmmommmmmm1morm ctr-sun damn-muey of flung-cup. Minuet-them Mfummmmumunummo-Qdcoflutdm Mmmmm. Hm,1anconlytho manmutuuoommmummmomoum moan" Wflflty should b0 mm, probably approaching unvuurorchloum. hmmdMon 0h acetamide propionamide ethoxyactamide monochloroacetamide formamide dichloroacetamide trichloroacetamide trifluoroacetamide EFFECTIVE ELECTRONEGATIVITY B‘UQHCDCLOO‘D’ Oe 2.-0 l I 1650 , 1700 1750 FREQUENCY m. (cm.'l) FIGURE I. EFFECTIVE ELECTRONEGATIVITY VERSUS CALLbuz-IIL rmm‘ mezawcy FOR A SERIES OF AHIDES 10 mumorordu. mumdthornqumiummt mtwmidomumwtmtmnmmytormcmm- «man. u u "out of tho induct”. «toot due to the china-1n. “on in chlorate-W0 the appetite would be anticipated. This may boduotosuucrfoottnddoh itcmmlongurboumdfim’atho notion mum um: the W1 vibration 1- duo solely to carbon man attaching 31m. Bone pet-1b).. explanation- tor the deviation at flu. Mutant}. will be mtionod 1n the alienation of Mon-fly values. It 10 of infirm to not. that a plot of effective Wnuvuy var-u tummy for the «tar. which correspond to we than was. nth tho «caption or propiomudo and othmucwddo. shared a unnu- 11m relation-hip (7). It on: b. concludod with away“ aromwmttho W1 “running frequency a linearly routed to the inductive effect or the “mutant groups to: tho ohm. aid... The integrand war or an infrared 000:1;an bum is proportional to the we or tho ”ginning (119910 mom for that vibrato: d the when. giving r1.” to tho absorption band. Th1. upon m we. to man by tho «wooden (an/ac), mm a :- mwapnmtamquw-mloomudmmg m partials: 71mm“ in question (25). when tho Whip mummmmwmommmmuom, flu quantity, (MI/00., for n mouthing nod- und :1, for a bonding MQMtumbondmmtomhoW. The correlation of the quantity, (on/60)., with know or eelouleble Ioleouler propertie- hee not as yet prov-n very util- hotel-y. The oonoept thet the change in dipole moment nth hood “fetching fight be interpreted on the boeie of fixed ehctronio ohergoe on the mold we tm‘nodiatoly shown to be insufficient by the large values: that in, great-2r than an electronic charge, found may... merenie e bond 1mgth for oertein multiple bonded loleouloe (35). In toot, these moaourommto luggeet thet the banned contribution of «merge separated roeonenoe tom, like (b) above, would explain the high value. or the chance in dipoio mat with bond etmtohing. Barrow (h) in recent studio. he! denomtreted e correlation betwem reeonenoe morgue end the intemi- tin! of the carbonyl absorption hand by “mating thet the resonance my «he to carbonyl conjugation in e measure of the availability of such e eenonicel for: ed 0)). Rooney (8) observed that conjugation In the keto Mid: increased the intensity of absorption. Figure 11 in e plot of the ebeolute intensity vflnee versus the Mom: for the amide. listed in the Tablee III and IV. The mthod of determining the eheolnte mtmity is outlined in the experimental notion of Part I of We thesis. The compounds hood in dotomining thin curve are] e, homemade) b, eoetesddej o, propionmzddo; d, Wed-moo; e, nomohloroeoetuddef 1', formation a, dichloro- Woe) h, triohloroeoetemide) and 1, trinuoroeoetemide. There are new poleible lourcee for error involved in the Mention of the ebnlnte intuition. Among the” ere the 12 b C) benzamide acetamide propionamide ethoxyacetamide monochloroacetamide formamide dichloroacetamide trichloroacetamide trifluoroacetamide HD‘OQFthOO‘W IIIIIIIIII TRUE ABSOLUTE INTENSITY £2 £0 | l 1650 1700 1750 FREQUENCY max. (cm.'1) FIGURE II. TRUE ABSOLUTE INTENSITY VERSUS CARBONYL PEAK FREQUENCY FOR A SERIES OF AMIDES 13 Macy end inteneity reprodooebinty e! the epeotmeter, the mount of netted-ed light preemt, weighing errore, loom due to evepcretion, purity o: the compounde, maternity end determination of the cell thickness, and the noiee level of the epectrometer. In comidmtion of these possible errore the accuracy of the inteoeity value: omenlybe named to be goodoithinplue «tame fiveper cent. The relationship between the obeolnte intensity end frequency 10 reoeonehly good with the exception of rem-moo, trimoroecetenide mo ethmecetmm. Theeeeretheeamethreecmmomdeuhichdid not follow the linear relationship between effective electronegetivity end frequmoy. It in felt that the me. effect dimeeed perimely ehii'te the carbonyl vibration of remade to e higher frequency, 1:, menu it to be out of crow in the frequency intemeity rentionehip. However, no pleoeible exploration on be offered for the dieegremt of the ethoaqrecetemide. Inflammatemide chow e rether intereeting divergence tron the linear reletionehip described ebove. Ite frequency ilhighuvouldbeucpeotedtronthelergeinductiveeflect ofthe trinnoromethyl map. However, en examination of the plot or frequency versus effective electronegetivity, Figure 1, me- thet the mm is not on high ee wold be expected. In feet, the tritluoroeceteMde bee the hig‘heet. intensity of w of the crude” whereas, the oppoeite humid be mooted. It is 1:0th thet enother component of the aural vibration is mm mm for the trinuoc‘omthyl group then for my group in the other emidee. the etrm inductive effect of the mopvillproduceenchlergoroipoleoomltothe cerbonylbood exie then ezv o! the other mp3. For this me e beaming notion of the groupe etteobed to the car-bowl group, even though not e lerge outpatient or the normal vibretion, my nuke e relatively mob lerger contribution to the intensity due to a change in this dipole. Bayliee (36) obecrved that in dipclar eolvonte such ae chloroform the intensity values of certain ketonce wore greatly increased above what would be mooted from e consideration or the refractive index or the eolvent. It tree claimed that in polar eolvonte such as chloro- torn there ere tun superimposed effects: on electronic component and an orientation component for which no simple theory cadets. Concidering ell feature it appears that there is e linear relation- ship betmen frequency end intensity for the amides investigated. The nejoriw of the amides can exert only an inductive effect with the ' exception 0: boncanide. In homicide the benzene ring is conjugated with the carbonyl group but nevertheless it ie in good agreement with the frequency inteneity relationehip indicating flat conjugation with another group does not invalidate the linear relationship of frequency end intensity. However, more are instanaea in the literatwe there other effocte emear to be operative. ml! (37) reported that in the ortho halOgonnted phenole the frequency of the hyclron'l group decreased es the intmeity decreased. m1. is, crtho iodcphancl has the lowcet frequency and the lowest intensity where“ crtho fluorcphenol has the highest intensity and higheet frequency. There 15, et the present time, no plausible explanation for this effect. mwammummunmw tummy. memfin-otorm, W.Wlflmmo WW' mmuwnqnmuumm.nmumm CHM”. hWMlfihth mmmwammmmumw. mummgumummmmwm uthmotm,W,m.i Mom-Mmm. Whom-um mmmtmnmmmmm. h. mmmwwuuummnamu mmummnwwmucmm wmmfmfl) ‘\c'-o" q-o A\cno ’I’ 3/ (b) (u) arm-nun. ztmuwmmmmAunn-m ”OSMOWMOIWWIWMOM‘RW Mdaflmotmommwotot-(dwO). muomumwuwywm‘m WMEWmothmm. “0‘8““ ”Amm‘ummnwmfimu ummmmwuuumguumuw mph-“thud“. rcnmAmuW 16 than offset. mid not mute-t themlvu in the absorption cur". For «maple, triohlomoataIddo than 1 Mia regal-16:: bat it. absorption our" in try-metrical. For the one: than than in no mm effect u in tarmac, ”We, 11me and manom- uetmldo the anthem). Ithaca-yuan curves W b: mutual. Hm, armouuowoionahmm,wmmmws peaks. Mam-Mmatmtadhymviu (38) tothaprmotan oqnuibriun hm muchtod and ”counted molecules of wetnido in chloroform solution. The more mm peak at 1678 on.“ 1. duo ummmrom,mmommmpeaku17ozm“ “mouthomsaoomodfm. Itmdmutodby Dad-nth“ in very dilute Iolutioa the 1702 on.“ peak became-u the more Mme. Aplntofthonolar uflmflmmtflcimtormhpflmm my chum-punt: duo £0 um adamant pod: 7m mum cumm- flu mutation that the ”his." intensity of tho peak: in W in m dilute ablation. ‘17:. running mid“ m m “W11 M m m mmumumuamtumohommmma mamadmutmmwmw m1 We: cum. who «at location a: chat mm ”almanac-mm. unmitotfihmmodpoud umuth-chdumthmmtmotwom uMmmmmmqumom-ymw a: the m1 absorption curve. Depth thou complicating tum 17 the relationship between Money and insanity of tho wbonyl ham loan to dopond, in tho undo, on the inductiv- oftoot of. the monument group» A va‘y interacting affect in obomod than 1 trauma atom to momma! on tho nitrogen atom of mono, 61, Ind momma”. The "In for B, the moat integrated intensity, decreases by mainstay 0.75 intensity units ”but the Money was no appreci- able chugo. Doria-1y the ammonia“ I111 not than the lam 13w "humanly W W and intensity of tho and”. Honour, u a tomato amp €119 mutation bomb. The mount: Money mam cannot be mum «on; cum-em typo. otoompoundonohumo,mmwfl~ommdu. Adamo: Immnoutnfihofmrpoduonoxnykmommtho Wtybyo.65 not. and W the Wbyza out" mumubymmmw muoawcbmam. htomootthomidu, m,mmhmumu mmwumwottnumuxmtmmmnm "lulu. In not, no «platoon of this on: be afford a an M use. mmntdoolvmuvorthydoomt. arablolm Wwoomzumhmmywmtmtymmm from when “In-nomad fio ohlorofm for thou comm: which we mono in both ”luau. 18 WI VARIATIOflB IN Fame! AND “FARM Immsm IN CHANGIRG mm CARBON TETRACRJCEIIDE T0 CE-EGZCFCRM AS SOLVE}. Compound “a" {’qu wmccotmoidc -9 0.21 E-Brommnochloroacctmfidc -20 0.25 R—Bromdichlomcctomido ~5 (LL-S NoBrcmtrichloroac ctcnidc ~15 0.07 Dichlomccotacddo «~11 0.2? AA...- A. ARA .‘_. —4—4‘ _..___ 4 ._._. T *7 WW *7 vv—vv— V—___. N‘— ——v w An examination of Table I show that no oyotcmtio clungc in Money is evident. The frequency clearance while tho apparent may increases in all ems. However, tho immunity change for tho trichlomccmmdc 1- qoitc mil. moo change. in frcqnmy and intmitw can qualitatively In related to change: in tho retract”. indoor: and dielectric constant of the median (36). Thor. 1. .109 com-- adorablo cvldancc that chloroform is capable of hydrogen bonding with polar maps Inch u the W amp (39.50). Such «rect- mmwwumumwmwwdw Mandy. Tho small change in intensity for tho H-bromtriohlorc- costume could be related to a Mo inhibition to W301! bowling with the chloroform oolvmt. The mix: object o: the pmont work m to relate coma ply-OM propertyofthcl-hromcompcmdocrthcirpumwutofluir chum-1M0! ”Wing om. mmmmwvm mmtmuauwmmmumm- tho Mn «not. or mm m it con to mind“ m1; flu largo: tho induct" «M of the Milan group the non 1mm in chm-actor to tho mimosa: to trauma bond. mt is, the m atom incrooooo in pooitivo char-actor with increasing mun afloat. Agooddulmrodoudllbonoododtongutm ”ability of othor orfooto bung prom vhich my inflame tho occlusion of tho Mutton reaction, nth aw... 20 Solvont CHCl -33 9.090 x 10 M 04 M H°IH 0-4 O ‘d¥f‘ l I I 1670 1690 1710 FREQUENCY (cm.‘l) FIGURE III. cmom ABSORPTION BAND FOR ACETAEIDE (INFRARED) ml». Solvent UHCl 1.021. x 10‘214 3 21 ORA 0.0 I l I 1680 1700 1720 FREQUENCY (cm-1) FIGURE Iv. CARBONYL ABSORPTION BAND FOR CHLDBOACETAMIDE (INFRARED) 22 Solvont CH0].3 1.172 x 10‘211 0.0 0.1 0.2. 0.0 A i I I 1700 1715 1730 FREQUENCY (om."'1) FIGURE 7. CARBONIL ABSORPTION BAND FOR DIORLOROACETAEIDE (INFRARED) 23 Solvent 08013 1.013 1.10'2u ‘i-IIH 0.0 I r I 1710 1730 1750 FREQUENCY (cm.‘1) FIGURE VI. CARBONYL ABSORPTION BAND FOR TRIORLOROAOETAEIDE (INFRARED) 211 Solvent CHCl 3 1 0.7 1 10¢»: MR 0.5. I I l 1670 1690 1710 FREQUENGI (Gm'l) FIGURE VII. CARBONIL ABSORPTION BAND FOR ETHOXIACETAHIDE (INFRARED) 0.0 25 Solvent 011013 7.550 x 10-314 0.0 T I l 1690 1710 1730 FREQUENCY (cm.‘1) FIGURE VIII. CARBONYL ABSORPTION BAND FOR FORMANIDE (INFRARED) .. .5' . ‘t'wsw *- 26 Solvent CHCl _ 3 1.082 x 10 2! OAS .0 HH 0&1 0.0 I ‘ l 1730 1750 1770 FREQUENCY (cm-1) FIGURE Ix. CARBONYL ABSORPTION BAND FOR TRIFLUOROACETAMIDE (INFRARED) Solvent 011013 1.177 x 10'2N 041‘. .4’h4 03-. 0.0 I l I 1670 1690 1710 FREQUENCY (cm.'1) FIGURE x. CARBONYL ABSORPTION BAND FOR PROPIONAMIDE (INFRARED) 2? Solvent CHCl 28 9.11.7 x 10-311 0.0 0.1 Holt-4 I g. 0.2 0.0 I I I 1660 1700 1680 FREQUENCY (cm.'1) FIGURE x1. CARBONYL ABSORPTION BAND FOR BENZAHIDE (INFRARED) 29 Solvent 001 9.326 x 10' M 0.0 O———1 HOIH §{. 0.3. 0.0 l I ’47 1690 1710 1730 (cm.'1) FREQUENCY FIGURE XII. CARBONYL ABSORPTION BAND FOR N~BROMDHONO0HLORO€CETAMIDE INFRAR.) 3O Solvent CC] 8.121 x 10’ 0.0 0AA. EFL. §. 0.2 —_I 0.0 I I T 1710 1730 1750 FREQUENCY (cm-l) FIGURE XIII. CARBONYL ABSORPTION BAND FOR N-BROMODICRIOROACETAEIDE (INFRARED) Solvent 001 8.010 x 10‘ Q;% Oé. 0.0 31 l I I 1720 17A0 1760 FREQUENCY (cm.'1) FIGURE XIV. CARBONYL ABSORPTION BAND FOR N-BROMDTRICRLOROACETANIDE (INFRARED) 32 Solvent CH013 9.381 x 10-314 7.9L. l I I 1660 1680 1 1700 FREQUENCY (cm. ' ) FIGURE xv. CARBONYL ABSORPTION BAND FOR PRENYIACETAMIDE (INFRARED) ‘1 awwvw_ . 5.1 a.) {P r. I”??? m The oorbomrl ebeorption bond for each or the compmmdo investi- atedeuployingoPmmnm-odolzldmbleben lettered epectrometer equipped with e eodm chloride optical mtoe. Anxedmtuldthofaoeicmveomhyedmltmghoepeetnl one udmuoppmxi-w 3.5 on". nae-apleeelluedhede WdOAWuueodetWoytheWmommthod, mean: mozmopodbywm end runn- (19) 1nd letec' modified by Sutherlandmdmmo (20). Inningtho interferencemeaothod mmwummomuomm. “mummmnuwnmmmrum mummcmommwhmwomum theeell. mmmmmmmmnmmm “mempnttod,eoecerdlmto,omnotthemmm “n.4etthemendnln1neeoebociooo. Suoheplotmee mntmmomothtmeiomcmmmna. MPfluMWu-opentedmmrdththe Mmuthentmoeell. m,1tnoletortoead toothereuenmoretheoolventehoeodoboorptlonthotthopreooeoe «mummomwmmnmmunm byeonmtu-ootoothonmupeetodtwooooMGmucnorthoeolo W o: the mm in momma o: the oouponnd being mung-tad. Incrdntocooreottorthiophmmtheepootrmtorm Operated with both beams open end maploying no rota-moo coll intcrv poeod in the reference boom. Atmophoric atom bondo me utilised to rotorcme for frequency calibration. A base lino of 90 per cent Waco we. need in all of tho dotcromuona. Chloroi'oz‘m was the solvent used. for tho dotoz'mnation of tho infrwod spectra of all the compoumo studied. In addition, vith certain cmtapmnuls, where tieir solubility pornittod, carbon tetra- chloride was used no a solvent in order to hwootigota affects on tho epoctra (3310 to tho eolvont. In this Lwcetigotion the use of both reegont grade and. Spectrophotonotric grads oolvcnto resulted in identical data 10.121111 oxportnental error. to Stair-.100, banzzmido and fomwido were obtained from matron Organic modem. Forrmdfio was freshly distilled each tim Just before it was used. Aeotamidc and bonzazdfio wax-o rocryetollizod reepootivcly from cfloroi’orm and voter followed by drying; in a vacuum dmicotor just prior to each tint: they were used. The preparation of the N-brono zoom, di, and trichloroacotamicloe are doacribod in the second part of this thesis. Shay wore rocmmtolliz od from carbon tetrachlorido, dried in the absence of any light under vacuum and ' “wood (21) for bromine imaéiotoly boioro being need. A11 melting point. end boiling points are in °c and are un- corrected . 35 {Men of ghmetenide (22) In o one 11m tingle neck flask, fitted with o 30 on. Fig-aux comm end dietillotion heed, were placed 136 3., 1.0 mole and 120 3., 1.05 melee of mm carbonate followed by the addition of 200 on... 3.5 who, of glacial acetic acid. The reaction More we gradually heated until ell the materials boiling below 150°C. had distilled. The mum: rote of distillation one not allowed to exceed 100 Dillintcro an hour. The reeidoe from the reaction mixture, com teining the crude product we poured, while still hot, into twice its volume or outer end nwtralicod with dilute amnion hydroxide to o phenolphtholein end point. The phomrlacotenide was recovered by filtration, recrystallized from water and dried at 105°C. for two 11mm. The amount of product obtained on 05’ 3., 0.63 m1... end 63 per can yield. It: melting point was 157-157.2°c. end that reported (22) for the some material ie 157°C. {aeration of Prop Egg (23) Into e half liter single 1100}; £10.81: equipped with a 30 cm. vigreux colleen end distillation hood were placed 1.20 3., 1.03 12301533, or emoniun carbomto mi 1‘05 3., 1.95 moles, of propionic acid. The tmmre of the reaction momma mo greaiually raised until all the tutorial boiling b.2160 230°C. Rad been distilled at I rate of adulation not in excess 01‘ 130 ml. per hour. The crude procfmct remaining in the distilling flack solidified on 0001ng and was recrystallized from benzene followed b; drying in a 7m deoaicetor over paraffin wax . Tho amount of product obtained was 93 g. , 1.27 moles, a 65 per cent. yield. It: melting point up 81.3-81.§°C. and that reported (23) for the some mtorial is 81.0%. mwmatimfiog Mint-goon otorzit‘c (23.2,) _ Into a half liter two nook flask, tho quantitios, 13:1; 3., 1.26 moles, of trifluoroacotio acid and 111.2 g... 6.1 mlo, of 2mm‘7rous 3061113: allfato were placed. To this a. mortars of 178 13.1., 3.0; moles, of nbsoluto othcnol and. SS 111., 1.03 mice, of cornmtrotcd sulfuric acid was added slowly which conned mfficicnt evolution of heat so that tho rocotion fixture we. to be oooloal. Following the addition of the alcohol acid mixture the rcoction fixture was sot aside for nine hours and than distilled on a steam bath. Tho traction boiling in the range SIS-56°C. was collected, mun with 150 m1. of cold 5 per cont cod-inn oarbonato ow: dried ovor 25 g. of calcium chlorine at 0°C. This crude product. was hon rwlistillod from phosphorous Nomads and the Motion boiling in the ranges 61-61506. Ina collected, clinched in .100 ml. of mammals ethyl ether and then mom go! was bubbled rapidly through this solution until no further predpttafim of product was observed . The solid ms filtered, recrystallised from ethyl ether and dried by moons of a vacuum pump to give a 70 per cent yield of pure product with a melting point of 734130. It: reported melting point is 75°C. ( 214).. 37 12an of 5m (smog (25) Innomlimthrunockmnkfltbeduthnm, reflux oondm Qnd dropping monolm placed one liter, 17.1 moles, of absolute ammltomohmcddod 1.6 3., 2.0 holes, of metallic comm-ammun. Mallettholodinnhodnnctedthc mamammommofidinmmuthmdzugu 1.82 mingotorudocthylohlmumumaddoddrogduonrtm WW. Stirringotthormflonmomeommdfwu mum). four hour- rollmm tho sodium of the holes“: arm uhloh the min: chlorido it. removed by tilts-man. The coding Wmmhfiuthmualmnporumotommuhm Wdfihthommu. mrmummmmoml mgmummmmmmwumcmt honing «- Lac-153%. I" collected. on. Mot, ethyl Wow... ”mummuummmmmuwu mmwmwo,wmhmpmm proud. ththomthuficmfimhadomodthomm.“ mm,mmmummmmum.mmdmm «nomination-stun”. mmtyummaumu 93.3g..o.91un..sowmmmaumm1mm. mwommuao.a-82.o°c. mwmmmmm ”amuse-52°42?» Into a half 11“:- um- nick nut, van-0M 85 3., 0.89 mole, 38 «emanate ”5.6031135 3., 3.0030100, ammo-M1. mumomnflnedlormhonnmmwuum Wadfizoothylohlomcmboinngtnthomgom-lhho. meow. rheohloNquaddod‘olSOal.otooncmmm “mu Woe Inc! all m until no further precipitation com. the solid add. no tutored, wry-mused from Inter mmuwhuungundunmm- manhunt. mmghtot wONM¢.,O.hSnolo,mdoorrupom-dtousowwtyldd Madam-We mm. It. mmnmmo'c. new mun. pommunammdu zoo-120%. (28). 2h. dichloronoetudde and tho mummo m M mmumamwwmmmwmm wmommmmommoutmmkdmbw momma... www.mmmuzswmnmm WMMMum-mmmum. morocco-ted um“ pom to! the umu9a°m non-that cum-d forth. mquMmWJ-ea". mWWn-Wnuvowomumm mmdMIunglammuniuuontro-um. “munching Wot BH39.5°9., m1. moms» momma Lao-owe. W B would be noted out the infrared absorption mobwmd m ind-panda» of tho 003nm and for the Wanna of the 39 uvonl man. That it, uhilo for a given nude different solvent. m and for it. multulliution Just prior to use, the infrared ubmption mite mo not affected. Tho amid. wuplu were mmtallind, dried, weighed out and median): Woo-red to a volumetric flask and dissolved in chloro- fora or carbon totnohloridor Tho ample cell was that rinsed aware]. times with the solvent being and, after which it not filled lath the um solvent. Tho «11m thonplaced inthe samploboenund thobmlinomudjuotod to 90 pa: cont transmission. The per cent tunmmon of the solvent in mod on:- a range or uuttioiont breadth to include an area 50 on.“ on author eido of tho carbonyl band mum o: the snide being investigated. The ma lungth of the light source no controlled annually in Inch u m that tho pointer mum come to equilibrium and an accurate reading of the par cont trumziuion could be made. Rudim- of. per cont transmission wore taken every 0.0]. micron over thin rungs. Thio moon" one then repeated for the amide solution, the per cant traumas-ion and van length were moi-dad, utilizing a hoolimutotQOpuconttrmnioaion. Frontheporcenttrm~ min-ion rwdingu tho ulna a: log. 10/1 was wanted for both the Iolvont and the Iolution. The value of loga 1J1 for the solvent was wmotodfronthonlueotlog. IJIm-theoolntimutmh rowing» ginthoutvnhooflogelo/Imototbemlm at tho undo or fi-bromouido. to A typical eat of infrared absorption date, for formamido, 1- ohm in Table II. The similar data. for the other emidoe end the H-bronoenidee inundated in the proeent etudy ere in an tppandix et the end of the mend port of thie thoaie, 'reblu XIII to XXVI. l-Zethod of 0b to wit the net velee of log. Io/I dne eolely to the oerbozvl group of the enide wee plotted ezeinet the Many in eeve numbere. A dietenoe or SO ethane lurked of! on eeoh eide or the eerbomrl Ab bend maxim. The eree nodu- the curve or the eerbouyl eheerption Whethendeteminedbyouttingouttheonneto edietenoe of $0 on.“ on eeoh eide of the bend uexim end comparing it. weight to the weight of the eene peper or know: eree. However, it wee room thet both me eeourete end reprodueeble reenlte eere obteined for the eree determinetion undem- eheorption bende by «in: en 'Ott' compon- uungpmm ammonuynmupioyod inuoheree deter-imam for the njority or the eheorption ounce. ' the Wanted eheu'ption intneity o! eeoh emide end ite N-brouoa Illa. derivetive m oeleuleted fro! the ereee obteined by the ebove eethed. Homer, duetetheueeotefinite elitoIJOnioi-onein the preeeet ark the “nation lee not noncommue 1h chereeter rennin; in velnee for the ebeorption intenuty, oelouleted tron the muctheweontieaome repreeentingonlytheeppemtinte- grated ebeorptioa inteneity, B. Ite velue in given by the equation, aw- .!.V-! _.. F's‘sflw-‘a "7‘ _ _‘ r“ nmn II INFRARED ABSORPTIOH DATA FOR FWDE Solvent CHCl,-0.0llj3m, Beee Line 90 Per Cent of Trenemiesion Net Carborwl t weve Length Solvent Solution 3 n V 7;: 103.10“ 10 91' 105.10/1 10' 16:. 10/1 10’ 5.680 1761 89 11 87.5 28 17 5.690 1757 89 11 87 33 22 5.700 1758 89 11 86.5 30 29 5.710 1751 89 11 86 86 ‘ 35 5.720 1788 89 11 86.5 80 29 5.730 1785 89 11 .86 86 35 5.780 1782 89 11 86 86 35 5-750 1735‘ 89 1‘. 85.5 52 1.1 5.750 1736 89 11 88 69 58 5.770 1733 89 11 83 80 69 5.780 1730 89. ll 80 117 106 5.790 1727 89 11 76 168 157 5.800 1728 89 11 71 237 226 5.810 1721 88 22 63 357 335 5.820 1718 88 22 55 898 872 5.830 1715 89 11 81 736 775 5.81.0 1712 89 11 32 1035 1028 5.850 1709 89 11 30 1099 1088 5.860 1706 89 - ll 36 916 905 5.870 1701. 89 ll 83 738 727 5.880 1701 89 11 56 878 863 5.890 1698 89 ll 65 325 3111 5.900 1695 89 11 72.5 216 205 5.910 1692 89 11 76 168 157 5.920 1689 89 11 78 182 131 5.930 1686 89 11 79 130 119 5.980 1688 89 .5 6 8'8 69 63 5.956 1681 89 11 81. 69 58 5.960 1678 88.5 11 81. 69 52 5.970 1675 69.5 6 88 69 63 5.980 1672 89.5 6 88 69 63 5.990 1669 89.5 6 86.5 80 31. 6.000 1667 89.5 6 86.5 to 38 6.010 1668 89.5 6 86.5 80 38 6.000 1661 89.5 6 86.5 80 31. 6.030 1658 89 11 86. 80 29 ll 7' V 7.. .: vr'm“ V ~.. .w .". ¢ 112 B‘e&$ log.(‘!°/f)'dv there 0 ie the concentretion in melee per liter”? ie the path length in omtimetere, To end I ere the incident end trenmitted radiation when the epeotrometer 1e eet at e frequency 01' \r' (29). The reenlte o: the oalculetione ere lieted in table III. The correctione which met be epplied to B, the epperent inte- zreted edeorption inteneity, in order to obtein the true integrated ebeorption inteneity, 1, here been dieouued by Remeay (29). . Thenethod uployedtocomerthtoidcpoodecnthebendehepe, the releticn or the elit mmtion to the extent of the wing correction, end the elope or the extrepoletion. Since no ooncentretion effect on dieoernible for exv of the «We in the concentration range employed in the preeent inveetigetion no utrepoleticn to zero concentreticn or peth length wee neoeeeery. fhe veluee obteined for the epperent integreted ebeorption inteneity, B, amen... the true velue, A, by the eo-celled Wing" correction. Ii‘ the bend ie coneidered to utmd indefinitely the reeidnel area under the Wine" my be en epprecieble treoticn of the totel eree of the bend, for while the ebeorption ie omen We frequency interval by which it ie ultiplied ie verylerge. Thie Wing" correction one applied by dividing the frequency renge 50 011..1 on both eidee of the bend center by one hell! of the bend width et m: intemeity. Tehle IV ehowe the correctione Ihioh were epplied to the epperent integrated ebeorpticn intmeitiee, B, to get the tree velee e: the integreted meorpticn intueitiee, A. IAHLE III 199mm IHTEGiATED ABSORPTION momma: 901 5083 11-11919 LED THEIR N-BRGKO DERIVATIVES Apparent Integreted Everege Compound Freqoonoy' Concentration Intensity Value of vmum") Holee/liter B,1n"em" a Aoetemide 1677,1702 0.00992 11.28::10‘ h.2lxl0‘i0.03 1673,1703 0.00909 8.218104 1678,1703 0.00930 8.21:104 1677,1702 0.01819 1.161104 Chloroor 1696 0.01106 3.92:10‘ eootamide 1695 0.0102h 3.95:10‘ 3.95x10‘10.02 1695 0.01783 3.97110‘ Dichloroet 1717 0.01172 3.79:104 Ioetenide 1715 0.01011 3.73110‘ 3.76:10‘10.02 1718 0.01530 3.77210‘ l'flchlcro- 1732 0.01885 3.372009 eoetemide 1733 0.00783 3.35110‘ 3.37x10‘10.02 1730 0.01032 3.h1x10‘ 1731 0.00369 3.36x10‘ Ethexy- 1691 0.01388 11.19210‘ ecetenide 1691 0.01157 h.21xlo‘ h.l9x10‘t0.01 1690 0.01h55 b.18x10‘ Ethoey- 1698 0 .011137 3 .911110‘ «Md. 1699 0.00719 8.002009 3 .98x10‘i'0 .03 in 001. 1699 0.01521. 8.011107 1700 0.01855 3.961109 Fcrnnmide 1709 0.01133 b.20x10‘ 1709 0.00755 8.2mm 8.2211061001 1710 0.00985 8.221109 triflnorea 171.9 0.0162? 8.02:10‘ eoetemide 1751 0.0081h h.lelo‘ h.0hx10‘10.01 1750 0.00515 8.06:10‘ 1750 0.01082 h.05:10‘ Propionp' 1688 0.00896 3.89110‘ elude 1687 0.01177 3.8mm 3.85x10‘10m 3.83210‘ 1687 0.01338 ”wfl. “—— Continued Compound Phenylo 1679 ecotemide 1679 1679 Boneenide 1678 1678 1679 1:10th 1726 acetamide in.001‘ l-Broeononoellé90 chloro- 1692 eoetemide 1692 h-Broeoecno-117ll chloroe 1712 eoetenide in 1712 001.. flcarcnodi- 1718 chloro- ecotamide flhflronodi- 1723 chloro- eoetemide in (me n-Bromotriel 1728 chloroo 1728 eoeteltde 1727 1726 1728 N-Brcmotri~' 1702 chloro- 17hh eoetendde 17113 in 001‘ treqheeqy vmccu'h Concentretioo holee/liter 0.01020 0.00510 0.01099 0.00835 0.0011 0.00763 0.00835 0.01096 0.00588 0.012h2 0.00908 0.00933 0.00866 0 .01069 0.00812 0.01077 0.00539 0.00898 0 .ooma 0.01007 0.00820 0.00971 0.00789 A 3.22:10‘ 3.20x10‘ 3.15:10‘ 2.96:10‘ 2.96x10‘ 2.88:10‘ 3.18:10‘ 2.6?x10‘ 3.59210‘ 2.53110‘ 2.63110‘ 2.62310‘ 2.60210‘ 2.58210‘ 2.52x10‘ 2.55110‘ h.h8xlC‘i0.03 8.06:10‘1002 3.87110‘ 3.19x10‘i0.02 2.98xl0‘10.03 3.1hxlo‘ 2.69x10‘ 2.6lx10‘f0.02 2.55x10‘10.02 ZAELE IV 88 1303 IHTBGRAIED.ABSORPTIOH IfifgflfllTIES FOR 80MB AMIDES Acetamide Chloro- ecotemide Ddohloro- eoetemide Trichloro-' acetamide Ethoxy- ecotemide Ethoxy-‘ ecotamide Formonide Trifluoron ecotemide PrOpiono amide Eonzomide Dichloro- tectonide ~ Phonyl- eoetenide H-Bromononoe chloro- eoeteaide R~Bromodi- chloro- eootemide H-Bromotri~ chloro- ecctamide AAA— ._..-._ 3.93 3.76 3-37 b.19’ 3.98 h.22 8.0h 3.85 h.06 Bob? 8.03 26 17 18.8 17.5 18.8 16.0 1045 18.5 20.2 15.2 12.8 19.h h.79 8.63 8.68 3.91 3.15 2.99 0801, 0801, cu01, 01101, 08018 001‘ 0301, fl fir‘. 115 Due to the neture of the ecetenide curve e correction of ten per cent III epplied, thich ie the everege correction indioeted by the work of Rum (29) for the frequency renge covered in the imree‘ti-Ib action or thie compound in the preeent ecrk. The velue or B for phewlecetenide one not corrected eince the ehepe of no ebeorption curve loggeeted there one odditionel ebeorption beddee thet due to theoerboxvl m. Thevelueeotfirorthechlorotorneolntiocect othe I-om deriretivee or none, 01, end Wow. Iere not corrected ee e consequence of the breedth or theee ebeorption bende enduaetendencytortheeeoonpoundetolibceteIreebronineinthoir ohloroforn eclntion. ‘ ' The ounce obteined from the plote or 103.10/1 "rue frequency (or the eeverel mid.- end their correeponding H-brone derivetivee Modinthieimutigetionmflmintigureemtofl. 80101113! 146 SWEAR! The ebeolnte integreted eheorpticn intoneitiee of e who or enidee end l—brcnoemdee were determined. me ebeolnte inteneity ie releted 1111me to the cerbcml frequency end the effective electronegetivity c: the ubetiment group- in the “7... end new. The ehepe or the cerbonyl ebeorption curve hee been dimeed intern-of the eteric etteototthenbetiheute. The higher the ebeolnte intensity end the lever the frequency of the och-bowl the leee ionic in the nitrogen bromine bond. 'f" L5- 1. W PART II MOI-{IRATE}! LED DECWOSI'HOK 331021028 0? BCHE l-BROHQAHIDES ILTR DEUCTI ON 147 INTRODUCTION The Kohl Ziegler reaction is e genera eethod for the intro-v emotion of e brownie eton in the ellylio poeition of en olefin, that is acommr e «on . cam-1,“ «- «ca . 030m. 6 Emu by the nee of en l-bromomde or imide under enhydroue condition. Wohl (1‘1th) in 1921 inveetigeted the reeotione or l-breno- eoetemide Iith olefine under cold, enmdrone condition. However, from 1921 to 191:1 only e fee (2.10.1510 addition]. reporte on the nu e! l-broeoeoetenide eppeered in the litereture. It .- not until 19342 thet the generality of thie routine: I. pointed out by Ziegler (15) end hie oolleboretore. They reported on e deteiled mined may 'ehich indioeted thet N-brononooininide me the but enileble broninetinc mi». The: further reported that h-bmmphthmnde mobbedelreedybenenninedbywohl (1:2)ueteirlyeetie1‘eotory am. not: compounds ee l-bronoghtetidde end N-hroeohmwdmphthel- inide were not very teem in thie me of nation. Since that time the Hub). Ziegler motion bee been widely en- pleyed by ermio ohm. The dieeovery or the eetelytie effect of peroxidee (hé), ehioh eede poeeible the brominetioe of em Weendelkyloheieeetteohedteerylp‘oupe,broedenedetin terthewtheeeopeeffliereeotion. Theudeintereetinthe 1:8 [Wee end iridee hee been oeeeeioned by both their peredozdceny elem out epeoii‘ioity end diverse reactivity. Thue under mild but different condition: the NW” end imidee reect to substitute bromine in the ellyl poeition (15) or to edd hypobromue acid (ELLE) er bromine (19,50) eeroee the double bond. Steroid chmiete (51.52.53) in perticuler have utilized the “Md” end iaidee. Schmidt (51;) end Kerne- employed the reaction for the brominetion of polyolei‘ine, cyclic ketonee end the eide chain bronimtien of elkyl eroanetie hydrocarbon. In eddition to their vuied bet epecifie reeetione ee brmineting egmte the Hubromenidee end ilidee’ eleo eerve ee eeleotive ouddizing egente (55,56) or verying you. end epeoifioity. Bu-Hoi (1) inveetigeted the reention a: fl-hromeuecimmae with e vide veriety of benzene end nephthelene derivetivee, notebly ethere , endebeerved thetbroninetion otbothringend eide eheinoooerred. mmmting oheree‘tnorN-bronoeeoeiniMdeheemerecmtly been weaved in thiophene (2) end in the methyl derivetivee of thiephue (3) iamhetheideeheinendmeleerbrmtione hevebeen ebecved. In new eeeee, et lent, the deeired direotion or reeetion (57) enheeeeu'elledbyeeteheteoreonditione. The feet thet the [Wee end ieidee etteck olefine et the eeaepeeitioeeereegeutegenerellybelievedtoreeetthrenghetree Mieduohmi-etmglanuchemheninrorthewohl tingle! routine (58,59,60). however, Mme melee? broninetion of both ”cutie end heterocynlio eomapounde ha been obeerred (1.2) it iempmbeble thtenioniemherdenieeleomretiveinthie eeectien. ‘flme eplnreleeclmniemie perhepe ehetter deecriptian or the eeehenietic woeeeeee imolved inthie mum, eince it ie likely thet immunidee end imidee like hobromeceteeide end lubmmmeeininide my reect by eeverel mechanical vaulting from We ee all ee heterolytic dieeocietion e: the reegent. Thee, em meptehle meehenietie eoneept or the Hohl Ziegler reaction met mount for the Mountion of olefine in the ellylie position, edditionofbrowmendhypobmmeecidtothedoublebondinelkeme, eide chein end ring brownie“ of eronetie end heterocyelic compounde. Further, it met eleo eecount for the ebnornel reactione each ee 7W1 ntetitution (61) end introchxotion) of the amide or 1:14. mm (62) into the product. Finally, my nah mhedetie concept ehmld eooeunt tor the ooneidereble difference in reactivity or each bromineting egnte ee l-vhromeenecinimde, H-bronephthelinide, l-broeogluterinide ad l-hreeohmhydrophflxennide in the ellylie eebetitetiee reeotion. the W menus-Moe Ill endu-teken to gein furthc inter. ntion concerning the netnre or the eechenin or the wohl Ziegler reeetim. A etudy Ill eede or the effecte of etructurel venetian e: thebreminetingegmtenthemntefenyliebrounetim. than. epproeehedbyeetndyotthebwuinetioncttoleene, eethieneteriel i! eepeble of both eide ohein end Helm bmzdnetion, under oompereble condition devoid ee fer ee poeeihle fro: eny cetelytio effect. Pertianer enpheeie he pieced on the develoment of enelyticel nethcde ~- ;.~" w a.” at... which uould permit 1: totel Wing of ell the bromine in the true-cu o: the reaction then the original em. 1. introduced intothereectieneyetuinthetmetthebromtingepnt. Both the photo end thou-mi ammu- or KW end inidee em mm: inveetigeted einee chewing eeuitiviw, due to verietimeinthe etmotnre, efthieme otbro-inetin; use, to each deeomoeitiene could ntuielly effect the netnre or the pollute in the Wohl Ziegler mention. 'i'f'fl firm-)1! In e ELL.) 1» yin-«Lu " Wren. B RIS’I'CRICAL Several methode for the preparation of N-bromoenidee end inidee have been deeoribed. The method (63) mt widely need involvee the reeotion of the enide Iith W in eqneoue elkeline medium. Another method (51.) imolvee the motion of the wide eith Immune end eilrer oxide in ethyleoetete ee e eolvent. A third mood (65) involvee the reection of hroanine with the mercury eelt or the emide dieeolved in chloroform. Ithe method (65) employed in the preeent work involved the reection or the wide with eilver oxide end bromine in triflnoro- eoetio ecid ee e reection median. The brominetion of toluene by l-bronoenddee end imidee he been recorded merel tinee in the 11mm. some: end Horror (5h) reported thet with I-bromoeeceinieide e eixty-{onr per not yield of beneylbroddeeeeobteinedmmhemoylperoxideeeeeddedtothe bronineting nurture. when elusive: chloride we ntilieed ee the eetelyet bmeyl broade tee not ieoleted but e «unto-one per cent yield of em or eonebronineted toluuee nee reelieed. In the ebeemee or e cetelyet, Schmidt end Kerrer reported thet hroeinetion did not occur. Bum-801 (l) eleo reported thet no hroninetion occurred lithoet edded oetelylte. Km (66) prepered I-bronoperflnoroe “com end K-brenoperflnoroglnteriude. When theee We were elleled to reect with toluene, only ring broninetion occurred. Bower, by inoreeeing the routine: temperehxre to ninety degreee 52 Centipede both low). bromide end brone toluene could be taunted. York (67) end hie oe-eorkere prepared the l-hro-e nonunion, diohlore, triohlm, mm, dinnore end triflnoroeceteudee end elloeed thm to react with toluene. The» invoetigatore report both ring end side chain brominetion and that the ratio of ring to side chain hromimtion depemded on the nature or the hromineting agent. The effect or the “metre of the browning agent on the results or the bromimtion reaction ee reported by both Heme (66) end Pork (67) m attributed to the electronegetivitiee of the momma on the e urbane uhioh in turn «danced the positive character of the bromine eton resulting in nuclear brominetion. Park (67) suggested e concerted type of W to describe the ewe chem hroudnetion of takene. Bloomfield (60) propoeed e free rediod mechanism for the enylio hromtnetion end pointed out that mm rent-renew could be expected in the reaction. The work or sweet (sh) in lhioh Lev-1e type eoid oetelyete were need mggeeted that nuclear brominetion mlted from en lone mechanim. Recently Bailey end Belle (57) duonetreted the effect of eelte ooprecipiteted with the hromineting egent on the neohenin or the termination reaction. They tom»: taut theee ulte mead en elmet eocolneive addition of Manna] m, added alto did eat exert toe greet no effect. However, it these eo- preoipiteted eelte ere rmed en elmet exolneive euhetitution of bromine ooom. 53 letweettgettenetfiepheteehedeelerthernldeeoupeeitieo ettheHMdeeerWeeheebeenreportedintheehedeel uteretureuptothepreemttine. amazon 5h DISCUSSION Themejorpertof thewrkoerriod outinthie etudymem- «med flth en investigation into the mohanien of the Kohl Ziegler reaction. The «perineum epproeoh followed three loin drama, the exudation of the dark reaction of the HM“ nth tonne, e etudy of the infrared W of the l-bronoemidee end their parent mdeeeithpertionler euptueieonthe oerhooylhend, endenmveeti- gauoe or the photochemoel end theme]. deoowoeition or the 3m- melee. In the dark mention of the Babromemidee ulth tonne it no hopedtoohtetn,the1engthottdnetorreeefiu.thetetelemn “Momentum, theretieeteideohdnterlngmum, end the effect of taper-eta”. ‘ Pro-the infrared Ipeetronef‘lhel-bmoefldellndtheirpu‘m nidee 1t nu hoped to a»... tee rm. first, the pounce o: the peeke for the eerhowl bend. Secondly, the beolute integrated ebeerption intensitiee end to relate theee to the quality or the We on e brunettes emte. This, it he anticipated, would uretheefteetotnrietdoleinmtnreontheoomue mm egent. The photochemical end ther‘l demonic: of the UM“ In much out with three objeotivee in mind. .In‘ltnlly, to m the relative rate. or {oration of mm from which the relative SS mudmtmuwu-bmmuboohmm. Rm,bmtheetrntetmebmmehmmetdm an». and man: u Mute the poeeibmty or ample: fox-letter: unmummammm' fluennorpertetmenrkeeeeonemdutheetedyetm eenpereuve mum 0: “W60 end I, 1‘ Wk main 111th mkhm. Rene mumwmmmmu mmmm.wonmmnumau. Inmates-unload. hath rue-ot- m £11110 mm. JWW. end Mr- hreuneted eyelohuene. Thelmmude we “we“ invite Wmmel,l'cdmwwum55wm Mobmtin. mmmndememm ummuuamunmummmutmwo m~mmmn.mmwu. Metam- meMuermfimnlvmthaWMehm www.mbomummmmwuumco: them-euthanasia“. OWN—“emblem. won-mmummawmmumm. nmommmmanummm Wthyefreemtneotuem. rebel-“ted ummautmmmohmmummmmw “Momeetw. _ «mommmmunuuwwwm Wmummummummumw, mmnflutwcemreetmmueneekm,m n. .K 56 Get-”We or chloroform It elee aunt-.19: the higher pereentege eteouvem,55.5peeeent,eecoweredtehh.7permtror mammal“. namrornmwm1mmmumm Wammmwepered,n1womnmaem bromide, 1.3.3“, end Minimumde, (mam. o, .. 2h. ammumaommaoiumnnzowomnem, mwmummummmw munofmeMMMonproduct. New” mummmummmmmm W. Wc,IWWmlohmmld-beuo~ wumamw,n.swomtozmymmuu W. m mummma. wepered tree phosphorous wwwMuMouMumtumlmu- .muwnmmummmmcunm. muouwwwauwopmmmm WeMWumeee-un’ed. Idea-Momentum“ “hex-BNIMIMIIW‘WMWW “cement-mum. ~ “www.mmumutmmmm mummuumwmumommumcm neglneeeetue. Ieheebeeeknunterereeedeeede,daeethe moth-not(1),untuowmumummdam mmWeIeJaneWmhtmdeeme-mm bronineting egmte. me work of Schmidt and Kerrer (534) dmtreted‘ the effect or percxidee on the reaction. The nee or permoee in the reaction betmm l-bromoeuccirmeide em toluene reeulted in eide chain brominetien. meidee eleo bring about on. ellylie brMnetim or olenne each on cyclohexene (60). It bee been reirly well octet}- liehed that reactions induced by peroxide, ultre. violet ligzt and high tomemture proceed tku‘oogh e free radical mechanism. It as dmtreted by Peri: (67) that the preeence or Leide type eoide in the reaction between H-brommccimmide end toluene caused ring broad-v nation to occur rather readily. The presence of occluded ulte in the bromineting agent hoe recmtly beam ehmm (57) to cenee ring bronmntion. Levin ecide ere ionic type catalyste end no ouch promote en iome nechenien. The fact that “Md” end imidee een atteok the ellylic poeition of olefine end the aide chain of toluene , the position generally believed to react through e free redial mechanieu eoggeete etrongly ouch e mohanin for the “0111 Ziegler reection (60). However, eince the eddition of bromine eeroee en olefiInc double bond (19,62) end molar mbetiimtion (67) with lhbronoemidee hove been domed it ie very probable that an ionic melanin ie eleo operative in this reaction. Thee e plural mechanien ie pox-hex): e better description or the proceeeee involved in thie resection eince it ie likely that the Wee end inidee may react by mural mhwim, remlting tron homclytic u eell e: hetcolrtic dieeocietion of the reagent. 58 m correct nechenietio concept will eccount for e11 the Mate ebteined iron the reeetim. thee, the tree necheniee of the Uohl 21.3m- reeetinn met coconut tor ellylio brocdnntion o: olefine, edditionethrominemeedoublehond. 3117110 ehiIteendintroc- auction of the enide or inide unclean onto en olefinic oerbon end mbetitction of broudue into the eronetie mime. Further. the W considereble differencee in nativity of each brmneting. egente ee Hmnccimnde, 'lchrmoglnteridde, fl-brcmophtluliuide end l-bmhexeludrophtheliude in the dime we a: reaction ehould e. accented for in the magmatic «no... ' Thee, themdyutheinneredebeorptionepectnotmtypicel hbhl new charlie mun. egente, eith perticeler reference to the oerbowl group, wee underteken. It we: expected that enw Wmuummmmomumumemm deetevec-ietioneinthe etc'ectereefthebrodnetinguenterite ’pcutelddeeri-idemeetremdtted throeghthecerbmlm «new. Iteeehopedtocorrelete theebeolnte integreted ebeorptien intensitiee, or the frequency, or the ruler erteneion oe- ei'ticieut e! the ecbonyl bend eith the unnu- in Ihioh the ll-broeo- nddee er inidee function ee bmimting egente. f the mmm'm mm «mm an expected to give eel-e leenre e: the relefive teed-min e: the NM” or mace teen-d: hon-um We» at the nitrogu to brodne m. 1m titre violet light Mood Wtione ere know to proceed through e tree mm melanin. 59 The third pheu of the investigation into the mechanism of the Wohl Ziegler reaction involved the dark broninetion of toluene et different teapereteree. It we hoped to be able to correlate the Invent of eide chein brominetion with the reunite of both the photo- chemical doconpoeition end the investigation of the infrared spectrum of the I-bromenidee end iniden. The inveetigetion of the infrared absorption epoctre of the amoe- end their perent enidee conetitntee Part I of thie theeie. However, engr possible correlation between those studies end the restate of the hroninetion of tolnme he: been retained for thie pert of the theeie. It we found for the H-bromoenidee end else their perent enidee thet e linear relationship meted between the freqnmcy of the carbonyl hem end the ebeolnte intemted absorption inteneity. Further, it we found thet e lineer relationship existed between the effective electrcnegetivity of the R group in the two noleoulee R-Ctgli. end ac’owm, end both the carboxvl frequencies end the obsolete intemted ebeorption inteneitiee of the enide end H-bromoenide. It wee expected thet en: electrioel effecte influencing the neture of the nitrogen bromine bend due to verietione in the etrncture of either unide- or icicle: would be trenenitted through the cerbonyl group of such commie. Time, ee the carbonyl frequency of the moo or N-bronoenide ehifted tonrd shorter were lengthe, end the ebeolute integreted ebeerption intensity decrmed, end the effective electro- negetivity of the B group in the RC 4m: etruotnre increaod, due to verieticne in the etrectere of the l-broeoenide, the tendency of the nitrogen hrodne bond to undue-go ham-emu cleanse Mn inereeee. m, n the eeriee mac‘gem, mfgm end cam’o mmMnmemwotm-a mourn-Ilia the order 0613:» a» £3901,- » @1301. endboththemelengthoftheeertewlfrwyendtheebeehte Wmmtynneedwinthermm angel. ’ 03913!- ) 001" . IftheeeeeeIerQ-teenbetekueeeteleeemeefthe munwmwommammmu mmmuwuwmmm» Muldflnthemtutmtofmmflmuth hhudthWethehefl. hermit-coffin mumumwethfmmefmm thtthieneemmleintemeteuoe. Atbothtapereteree then-needcueebemed.‘ mmumnmnmuv. mov‘ manna omlmamo magmagtmwawmx . mnmmmnh mace. W mun neat mm a. . - ”W“ A _ M u 1;;- ocz.c’ «m 55.: 58.5 W°m 75.0 50.3 ce,m4°-omr 51.7 8.9 mmn.¢u1eueendo.05uhuwegd. The eoler extinction eoeffioiente of the eerbowl bend of Nahum mono, di, end triohloro‘ecetenide determned in eerbon tetree ehloride inoreeee with inoreeling effective electroneytivity of the o yea, with decreeeing we length end with deoreeeing ebeolnte inteyeted e'beerption intenaiw. rm, 1f the non:- extinction «efficienteftheeu-henylhendeenbetekeneeemofthe tendenoyof thenitrogen bumnebend toendergo heterolytie dined. etionitmldheexpeetedthtthel-bromeoerehflmthe higher eoler extinction coefficient enld give the W mount of heterolrtie dieeoeietion. com-reel: the levee the melee nineteen eoeffioientthe yeeterthetendmeyforhenolyueeleengeefthe nitrogenbreninebond. mmemmmmmunmwmmn order thet the unlit: of the Bahreneeeide, ee ohm egent, unlabededeeedfroutheepeetrelmertieeoftheeme. men. iftheeenetrmdinwmeefewelpeopertielueheem Mm, ebeolute inteyeted ebeorptien totality, Wytivity eftheudutiteentereolereoctimtioneeeffieiuteeietedforthe mdemtheiwmdeitmldbeeuiertomeeehm tieeietheendetheeieiteI-hruoderivwb’eeeiheletterm herediffieeltteebteieeeem. Mummpeoeldofm dwutmuaumyormmuemotm ingthegditydthelmuebmem. The ”matheebwewwfemdfereheweem wingteMrI-Ibreee-idee. Theeefiowlfrequeneyforthe 62 wmemiuIWdcinuveth-hemem fine ebeelute Meyeted eburptien infinitive. were met: 1mm- for thel-bmthenforflnpmmdu. the literetnre bee e ye“ doe]. of infer-Luca concerning the photochemioel Widen of e tide review at abeteneee each ee «mm, (78) «mm dioxide (79) end hydrom mm. (80). m,nere£meeoemuteundinehiehehepheeoeheeieelor then-ml dmmeifionet the taut-Wand manhedbeaeudied. Mmmohmeemmedquiohtlightuehuthe Man hem toluene end chlorine (31;) to give beam emude, boned chieride end beneatriehleride ere gunmen: believed to weed byetreerediceltypeefm. xe-empeduneehepzme- ma end/er w emu mat-e e: the lam-enema mmmomunumawamottbew“ In. mic}: their Mt. tend”! M honlyfle Wm 01' the ummmmmumm. mere-museum»- Menudthernideeoepeeiueammwnmcthe W median teed, end the tenure retee o: deeeupeeitim dflzelMdumldmbedemfizemoftmum “Maine. méwuummmvwnuenhthemry ughtmcewmdmdweuflmmeduthemhmp. mmmmmemwuummmbyw umwommmumwimmmomm- Mew. mwmammcbmu Need in Inch «magnesium no never found, end on manned 63 redietion for long periode the bromine ebeorption decreased showing that lone bee of the letter wee occurring. Undoubtedly mm and enri‘eoe catalysis very probably play I Motion in the deeomoeition musing eone of the irregulerity in the observed reunite. A light eource of meh greater inteneity, each ee e high pressure mercury ere, ie neoeeeery to facilitate the decomoeition of the H-bmnoenidee. inorereflnedupa-imteleyetatoprwmtloeeeeerhrondhotron the emplee end the eliminetion or equalizing or oxygen end enri'ece effecte ie required. Reliever, it an be eteted in e. mnlitetive m that H-bmmnnochlaroeoetedde undergo” bomlatie fission of the nitrogen bromine bond et the yeeteet rete to produce We, end B-broeotriclflmoecetezdde ie the donut to undergo each rupture of the nitrogen bromine bond. Thie etetaneent ie beeed on the chem- euon thet e eolntion e: l-brmmhlomoetmu he the first to develap the brouine eolor than eolntione e! the I-bromo, none, di end triolflnroeoetenidee of comparable concentretion in carbon tetrechloride Vere eat eeide in ordinery rm light. me H-hromotriehloreeeetunde he the lent to «level» the color aha-eaterietio of hrofine. This would indioete that, ee expected, the miller the electromgetiviw ofthefiyenpoi’theRC-mmrthe yeaterthetmdeneyi‘arhomlytie tieeinoi‘thenitrogenhroninebond. 'rhie ieingoodeyemnt with the infrered date in finch the reletive tendenciee for 11ch all batmlytio mpture we hweetigeted. Than, it eppeere, baud on theee obeervetione end oonclmione, this only en inductive effect ie operating in controlling the mmer in which the nitrogen to bromine bond ruptures in the reaction of the E-tmomoemiéce with toluene. Although no quantitative éeta wee obtained from the photochemioel and themal deoonpoeition ctmliee of the N-bromemidee amoral 3131111" cent obeervetione were made. A etudy or the curve, Figure m, for the deoorzpoeition of H-hronotrichloroeoetmide ohm that initially the rate in elow, then increaeee to e etearh' rate, end then taper-e off. m- type of curve is characteristic of en entooatelytio type of reaction in which the products of the reaction catalyze the intinl reaction. This mtocetalyeie ie demnetmtcd more conclusively by Figure XVII which is a plot of the 1415 nillinicron bend of browne ageinet time for the deconpoeition of solutions of l-hronotricmoroc- «etude in carbon tetrachloride and H-bronotrichloroaoetenide plne free bromine in carbon tetrachloride. Both eolutione contained the who concentration in yen atom of bromine. Figure XVII ehovs, by the increeeed elope of the cum representing the decomposition of the solution of the h-bronoemide and bromine, that the presence or broflne enhance the rate of decomposition of the l—hmmoenide. The eeoond observation concerns the absorption peak of bmrine in carbon tetrachloride. Thu peak eel reported (77) to he at MS nillinicrone which wee confirmed in the present etudiee airing the preparation of the Beer's law canoe, Figure XVIII. However, such the not the cue for the hmuim peak arising from both the photochemical OPTICAL DENSITY 0 (I 0 0 0 s‘ C 0‘0 I 1000 FIGURE XVI. OPTICAL DENSITY OF THE BROMINE ABSORPTION BAND VERSUS TIME 0 0 0 O 0 TI 3000 TIME (minutee) OF IRRADIATION 0F N—BROMOTRICHLOROAGETAHIDE 0 65 l 5000 66 A N-Bromotrichloroacoggmide in 0011+, 9.32 x 10‘ B A Mixturo in 001 of Bromine, l..66 x IO‘AH, and N-Bromotri hloroaootanide, 8.39 x 10" , A Total of 9.32 x 10‘3 em- Atom of Bromine OPTICAL DENSITY P H A A C A u 0.01% V. l I 2CD 500 800 TIME (minutes) FIGUE XVII. OPTICAL DENSITY OF THE BROMINE ABSORPTION BAND VERSUS TIME OF N-BROMOTRICHIDROACETAHDE DECOMITION WITH AND WITHOUT ADDED BROHINE 67 and thermal decomposition oi‘ the N-bromoonides. In the doomoooition of the N-bromo none, di, and tachloroocotnmidos the initial peak to appear as at 380 nilliniorons. This pool: gradual: shifted to longer a length: to the decomposition precocded until it reached a value of hC’B-MO nillimicronc. it this we length tho pool: roach-oi its ammo intensity and did not shift mrthor on prolonged irradiation or heating. In tho docommoition of t‘oa sane N—bromoamidos in tho presence of bromine the peak, boforo irradiation with ultraviolet light or before heating, was at as millinicrons. is the decomposition pro- coodod tho peak incrcosod in intonsity ondohii’tod to shorter mo lengths until it reached it reins of hos-4.10 uninicrons. From this point on no further shirt was observed on continued irradiation or booting. The above data. suggests that tho bromine is cmplozoci in some mnncr in the carbon totracflorido solution of the" X-bromoamidc. molecular complexes of tho hangar with maturctod hyfirocarbono, alcohols and others have boon known for some tins (81,82,83,E.‘4). Iodine in particmlar has been reported 81;) to form a one to one mole- cular complex with ctr-3'1 alcohol in bonnenc. Cryoscopic moanurcmonta supported ouch a. conclusion. '1'th , the cosumtion that bromine is complcxod with something in the carbon tetrachloriéo solution of the N—bromnnid s zooms very reasonable.“ The question nntm'ally Briton u to tbs nature of the bromine complex and the extent to ouch it is oonplcmcd. From the above obsorutionc it can be concluded that the bromino ie conclmd rith something which is formed as a result of tho photochsmical or thermal decomposition of the N-bromoamido. That is, the bromino peak of a solution of tho flibromoamido and bromine in carbon tetra- chloride before decomposition coincided with the hlS millimioron peak of a solution of bromine in carbon tetrachloride. Howovor, during the decomposition.thia peak shifted to shorter wave lengths, as low as hCB-Llo nillimiorons. This shift could.bo canned either by tho_ complexing of the bromine with something being fornod an a result of r the decomposition of the Nébromoamide or'by tho appearanoo of a new peak clone to tho hl§ millinicron‘band tor'bronino loading to a shift of the bromine peak toward the noIPpaak with n Iinglo combined resultant peak. In the decomposition of tho Nébronoamidoo the first peak to nppear an: at 380 millinicrons. Tho solution at this time had tho brown color characteristic of a dilute solution of bromine in carbon tetrachloride. There was no other peak present between 350 :nd sno nillinioronu. This peak on. attributed to the bromine tied up in some manner with another product of the decomposition. The fact that tho peck shifted toward longer wave langths until it reached a maximum of hog to hlo millimicrona indicated tnat the final and intornodiato peak uxvc lengths could'bo attributed to a combination of tho two packs nttribntod to compluxod and non-complorod bromine. That is, the first bromine resulting from tho decomposition was completely comploxod but an the decomposition proceeded nonocomploxod or free bromine was produced. 69 The nature of the complex is unknown. However, since the bromine in complexed with another product or the decomposition some reasonable lpoculation u to the nature of the complex can be offered. The thorium or ultraviolet light induced. dooonpooition of H-bromotri- ohloroaoe‘bnmido is the simple“ one since in this case there is no pocsibility or any bromimtion motion occurring. The initial thorn}. or ultraviolet light induced dissociation ounfibo expressed an 11° 0° cc1,c «mar u 001,0 4m - o Bro O 0 Br- . “1.0 4191' ‘A 001.6 *1! . 0 31" F This lattor flop was shown by the moron-ed “to of decomposition in.%ho pro-once or'bromino. A bromine oonoitisod reaction is one in thioh the initifl. step would be Br. 3-K 231'. A chain termination nap could follow o° o° - 3° 2 09.1.0 4m. -,-. 001.0 4mm. -ccl, . R is with thio him typo of (someone that. the bromine could be ouploxod . ° 49 o0 P I I cchc’mmmo 4:01, 0 Br. --~ 001,0 «mama ~00)... Br. Ono possible stmcturo of this complex may be 7O 5" s‘ /Ojn . O . .Br\ pounced bromine CC]. .0 . 5" oOeeeeg M 0 m0 . \“a‘ .6/ 3 Eu, The feet thet the bromine peek doee ehitt oeete eone doubt ee to the velidity of following the rete of deooepoeition of Inbronoenidee ‘ by bronine ebeorption a us unincrone. ‘ The experimental evidence for the above epecnletion ee to the relative tendency of the l-bronoenidee to undergo heterolytic or homo- ]:tio tieeionofthe nitrogenbrounehondnemrenyuebeeedenthe eotuel hroninetion reaction in thich the individual l-broneelidee eere employed ee the broninetina egent. The reeotione we errenged eo thet they were carried out under identicel condition. Toluene we choen u the compound to be etndied in the broadmtion eith the I-hronomae eince the prodnete of the reaction ehoe both ellfiie end nucleu- etteck, end in eddition ere eeeily ieoleted end enelyeed. The mount of eide cheinhrcuimtionne tekentobe eeeuureot the mount of hoeolytie fieeion or the ultrogen bromine bond. The dih- ference between the wt of eide ohein broninetiou end the tote]. treeinetioneeetheeeeuntotringbronimtionmichmeeeeeureot the mount ct hetemlytic tieeion of the nitrogen bromine bond. 71 Jiueuqfllgeeeeoidpige .398 H15 Yen-533%.aebflmn .gglflflg‘egfifi «.3 dam . 9mm 4& E8 .3. e33 atofl #8 1.3 v.3 3.." long 3.5 .3» .88 a... 9mm HR. 98 «Am 3858 34339.3 8 nae-858 tea in I... 8.0 SA 53 .35 3 so . eg 3 82:6 no Staging 66 3.3 «to am.» 33 33!; . muéu 8% $43 8.3 333w ‘ 83.3 an 8.3 $.mn «Qua m3“ 752.. seats 38155.33» n .. Qua oé md 55m 5 8385 we goofing you can wnéw 0.0m 0.0m 0.0m osgeflfieaauw .3qu mos mos. mos so... .38.: .1 mm; .u 5.» .u 3.3 .u 8.3 A. .3 I33 «.5 .ame. 08.3 has. 9.8% .3sz #8 2'3 33.5.38 £0008 Rd 353%! E S mug mun: §h bu 305% E 8 magm erg: 72 .8533?» .850 23 we escaeeuenauauneouelefileon .eofieoeaehgoaeuoe‘eeoaeeu e55 05.8 confined we 33156.30. mtm .5 «o «0.4 .833 5c. eggflogfififz no 8382 .5 er I" mém . coma 3.0m ~13 £80 hem uni-Hen gem 0.4% «.3 0.3 0:: 338380 «30 .30 030 .80 9mm 0.00 dam 0.00 3558 3838880 3 c3558 080 .80 0.8a 0.3 0.00 m.& . 838.0 no 33008 0.80 80 2.6 as.» 000 m»: 088 33.30 00.3 tum 3.5 Sin “gnaw 50010 no 00.0... 0m.“ 3.: m0.m 25»: 8.5330 30.?qu 00.0 00.0 an... mmé .588 or; no 35330.; 00.0 3.3 ”0.0.“ 00.0 0804 00383.3 308.50 mo 83753.an mg: 0.0... 0.00 0.00 280 5 05.» 838.0 00.00 0.0m 0.0m 0.0m 38358.3 53.0 m0.0 8.0 m0.0 8.3. £85 2n! mm...” .3 4.3.0 u and.” .u 5.5 2? .3 a rims t rumwzm 30-00 twig“ unamwp aflonmflmot .. 1 «80‘ 0.5.5.95 1 co 0e .. 00 g i L! $11 L§I 7 .003 S 000%.. a: 05 02.2000 09. 00038. no 005.38% 00.» .8 0.550 E 0.5“. 73 robluVIondmmuothormuon-otI-bmm, d1, Mommaootmidoo and hm with ooh-no oi m durum tap-am, 1.050080%. Wmmumuwwnm «maoamdummmmomammmmmd bo pomporod. Tho nation of tho Waco nth toluono oi 60°C. mo manna-0mm. nomuuudmguoomooot oolorohoncoofronoloortoyonn,uhmtorod,ondhookh you“ ogou. Thu-ovum «0111“.»qume during mooo mum. Tho [Wot-n1.“ Ibo-o6 tho largo“ mm, 91.1mm” o: troorodiooloido mun-Influx: and tho aunt mount, 8.9poroom, or 1.0310 «mm». Tho momma. ohm tho who“ want, MJ per cost an. Mum-unnamed mum-um 52.5mm, 0: mm. mama-mummmmmm and mum: «to. Tho WM than“ mount: m. oloctronopuuty um, on! W Woo W M l-bmtriohlmomdo would ho tho non may of flu Waco u man-go WM“ 0...... or m mung. brontno head and mo WWW. tho loom mo}: to mono hotorolyue Mnofthooonobond. mWI-ounoofthobmuon- atmmmonmwnummm ' tho x-brommmmao ohovod on. mm amnion, 91.,‘sporoouh, ummmwmmm, 3.7 per cent, or polybromtod product Tho H-brmchlmoomudo, 7h thich mo tho grootoot mount of oido chain lamination, ohovod tho mlloot, 78.8 pom cont, convex-lion to monobromimtod product and tho lax-gut mount, 21.2 por coat, of polyhromdhotod product. mu, tho groator tho lid. choin broninotion tho noro polyhronimtod product. Tho nth-1.1 balonco for tho motion: carried out ot 80°C. on at looot 99' por cont 1:: :11 coon studiod. Tho rowtiono at tho l-bromomldoo with tolumo carried out ot 1.0%. mo moved to pmcood for mat]: minty-ton:- ham-o, 1: which tiuononoottho noctimmoaomploto. Thom neuronal“ we found in tho noctiono at tho 30mm with toluono u 1.0%. u had been chomod at 80°C. Thot to, tho oono ordor no ohoorvod in tho ntio or oido chain ond ring hrMnotion of toluono. Tho Nuhmmmmchlomotmm mo tho highoot want of. lido chain hromlnotion ond tho mount mount of ring hrondnotiaa. Tho l-brwn trichlorooootoudo mo tho mnoot mount of oido chain humiliation and tho hrgoot mount of ring hrominotion. 'l‘ho want of “do chain bromnmon nu Inch looo for tho motion ot W’s. than tor thooo at 80°C. rhooo ”mu were one in amen-m. with thooo prodiotod from tho tux-trod and decomposition otudioo of tho brmimting agent-o. Tho rolotivo rateo of. reaction mo oloo tho mo ot ho°c. ond ot 80°C. that 13, tho ”action of. tho l-bmmtriohlmooobuddo with tolnom at 80°C. on complotod in 2.5 hours; mm, tho l-hromahlm— Mo rooctionuutho Wotthouomdiodondnocouploto only ot‘tor o. twolvo m ported. n 1.0%. tho l-hromtriahlorooootonldo 75 ooootionoooWJporoontmlotoofWthmoufithoI-bom- “Momma mutton woo tho hoot amploto, 15.9 por out, to tho mo pound of tino. fhomtintorooung mummonmthoroootionoomiod out .om°a.mtmrmmtmmmmmnwmm otthormttmotthol—hmuthtflmo. Inthoooooo: WIWJMMO ”woman-macaw. mmnWmmwnmtor-ormomm. In tho oooo of tho l-hrmfichlorooootmido 8.6 pot «at no obtoinod tothotmorrroohromno,ond1nthocooootthol~hmmh1oroc Mao 9.9 montnodotorunodintho tonottroohoomo. than, tho mom. trout no thot tho roootion Ihioh ohmd tho torn- monotthompcooatortroohm govotholorgorpoo coat of oido chain much. In too nation a 1.0%. tho notoriol holonoo on o nou- low, 85 por out. no. ooo duo to tho dooompcoitim of tho moontod [Mo am- it hod boon loolotod and hotoro it no only-ad. tho troo 5mm tor-nod echoed loo monito in tho iodimatdo do‘tom'urlm notion of tho W H-broaoonido. By roduoina tho bromino with munitions! Wag tho Hmondoocorroctimmld ho oppnod on thot o not-arm bolonco of 95 per cent on ohtoinod. rho roooflu or mloculor bromino with toluono ot 1.0%. and ot 80%. gm 89 on: 9h pu- cant, roapoctivoly, of oido chain Intonation. Mo no o highor nold of oido chain brodnotion thou any of tho 3W4“. Mo oloo gave o higher pacentogo of mnobrominotod 76 product, 95.6 por cont, thou om of tho some. ot both 1.0%. on: 80°C. the roootion tioo for mm with tolnono ot 1.0%. no ohorter than for any of tho l—hromoonidoo. it 80°C. tho I-brouotri- ohlorooootomido motod ot o tutor roto thou mimic bromno. Thotoot thotthorouohroninoprooont, oftoroporiod of twenty-four houro, in tho ooootim oixtnro or l-hroootriohlorooootono ond tolnono ohon «nation: on at tho fi-hronoonido hod roootod, oouplod with tho toot thot tho roootion of bro-lino with toluono no oomplotodinlooothonholtthottimootronglyouggootodthottho hrooinoi‘mmdinthoroootionottholrbrmooidolith tolnonom completed. in oooo oonnor. It no ohm in tho dooohpooitioo otudioo of tho H—hromooxddoo thot hronino orioing oo o rooult of tho dooonpoo oition of nah commando no ooopioxod um on unknown product brood in tho docowooition of tho 3W“ but not with tho lottor itoolt. It io not than ohothoo tho hmoino wold ho nominal oith thooddoniohooothobyprochotolthomtioaottohouohy tho Kohl-cocoon“. mu omido could not orioo tron tho dooaupooitioa of tho R-broootrichloroocotoxddo in cox-boo totroohiorido oolotion. Pork, Goodwioh, Lynn and Loohor (67) omiod out o otudy of mommumottolnmoithoorioootl-hmnidoouhiohin- olndod tho ham-om lane, 61, om. triohlaroocotonidoo. Tho "out; of tho brominotion of tolnono prooontod in tho prooont work oro in oono dioogroooont uith tho doto 0: Pork ond hio awoken-o (67). robloo VIII m I: who tho obviooo diooroponoioo. 77 TAKE VIII $st OBTAINED BI PARK on m BRMXATION a? TOIIIETN‘B Hm! THE Immwunas (67) Brodmting Conversion to f * ism 6,3,3: MGH‘CH, comm.» for Cont Poz- coht Poz- Cont 031,0 has: 58 17 83 magi-hm:- 61. 62 38 ,’O 33,013 4m:- 70 82 18 w ‘_ h *5: M“: o w I“ w __._.. .. A W. J um... I): RESULTS (3" THE BfiGiflHATIOHOOF MUEh’g WITH THE. H‘BRLMUBIIBES .u' 80 o. m 1.0 c. *3 0:01.. ‘L—fl—ofi 5;?W Brominoting Tagoroturo Comoroicn to Agont 0. $1?an 81063.63, Canaan,» Por Cont Poo- Cont For Com ,0 . 091,0 vmnh' 80.1 91.3 52.5 h?.5 cm1,c”2mmr 80.0 89.6 50.5 19.5 ,0 music 4:218: 80.0 78.6 8.9 91.1 .49 8013b 4333' 150.0 68.6 85.2 113.5 01m.ch no.0 5.4.1 75.0 25.0 CHfilceh’HBr 130.0 69.6 51.7 148 .3 MA _-——— A A .___._ A— ;_._ ‘ .-- 3 WW w '1... w WWW—ww— fl“ It can ho loan from those tabloo that tho diug'omont 1191! in tho rotio of oido chain to ring brominotiom by tho Bohr-0mm ond trichlnromotonidoo. Tho work of For}: ond hio writers indicotod that the hohromtriahlm'oocotmco govo tho highoot rotio of oido chain to ring hroflnotion, and that tho B—hrommnchloroacotomido gavo tho loooot rotio o: oido chain to ring Nation. The rooulto of tho work prooontod in this thoaio m :uot tho opposite». Tho N-bromotrichlorowotaznfldo gave the lowest ratio a: oido chain to ring hromimtion, uhilo tho H-brmmwchloroocotomido gave the higzoot ratio or side chain to ring bmmmtim. Tho emporium“). «Minna Ian-o Mt difroroxtt. In this work tho Mambo ova-o corriod out in content Woo-am botho at 110°C. and 80°C.) ohorooo, in Pork'o work tho roootonto mo mind prommhly at room! mama and than hootod ot tho rot'lux thpmturo of mm to ohm commotion of tho motion. It seems highly mwlikoly that thio diffomnco in conditions could account for tho diocroponoy bottom tho tomato. It io diffioult to offer o room- ohio summation for tho (Informal bottom tho two who or auto. Pork (67) routed tho oboorption cooi‘ficimt o! the 3-H fundmtol hand at 2.93 n to tho hrmlinoting activity of the nitmgon bromine bond sud found that the larger tho oboorption coatflciont the motor the mzmt of ring bromimtion. Tho aloetmnogativity of the '2' group 01‘ tho Ralf-HEB! otmctnro did not ogroo with the bromination 6‘“ o 79 The bromjmtion data presented in thin thesis and ohm to be a mama of tho brommting ootivity or the nitrogen bromine bond as correlated with the molar extinction coefficient of the cm'bonyl band of the E-brozaowldoo, the absolute integrated oboorption intensity of the whom]. band of the momma” and their parent modes, the wave length of tho carbonyl band peak of tho H-bronoanidoo and their pox-art mm“, and with tho effective dootronogutivity of tho "3" group of the R0 21%? and RC fun, Matures. It was {mod that the greater the molar axtlnction coefficient the lower the absolnto integrated nboorptlon intensity; tho ohm-tor the wave length of the unbound band and tho higher the effootivo electmnogaitivity of the ”12" group, the greater the mat of ring Maturation. The carbonyl group no chooon for than measurements bacausa of its relatively mgr; absorption intensity, and. in particular because it no felt that any effects of Itmcturo oontflbuting to the mechanism of the reaction would Hanna» thmelvoo 1n the carbomrl groupo In amt with the oat: from the bromination of toluene at 80°C . and at Lo°c. the following mechanistic schema appm reasonable. Bm.’ ti, o o ’h o " o 0 new: RCI-an‘oox’ 1319 0 6635611., .4- (Manson; ) 4° .0 [Bx-06115033? 9 ac 4139-”- as com. o magmas Bronx-Lotion hi; :1 jgadlaal I‘locmmm O ’0 I, I RC Mr --" RC dfli-O‘ Br. 1"- ‘vlith H-bromoamides o O I M’s-NH. o Canaan, : Roz-HR. 0 coHoCHa' 49 CSHLSCIiz' 9 RC 4m;- --~ 0518115 3.23:- + no 4% With Brooms. 4° 43 Br- 4» RC chi-{Sr --|~ EC 4311- 9 Br, Bromino Sonsitization w Br. 9 A --3 [.1 Br. 1 Complex Fomation Bl" 4- CglgCl-Ia 2 06858.?{3- + H Dr Bf. . GeBeCE’O 4". Gafifit‘SHIBr §' 370 0 HBroRc-lmar «Ir 33.413.03r. Examination by the Couples: [A BI") «I» 0&5621’3- ~1- A o cggcgafir o Bro 3 can. " [A Br.) [A m- 1 . m9 [A Brl®+ £4- cfiHfiCZI, --e.- A + BrCGIL‘CI-z, o H Br Chain T Mution Bro 0 Canaan,- --b 83241503133:- 90 .0 EC «an. «at RC firm!!!) at! 81 rhommroootqormthoMobrom-uuottolom hymn-woman. ThoMondtmrthotopomthoMo ooh“ roprooont tho prim hotor’olytlo cad hmlyflo «mention of mommmmum. ThotourthotOpthrmghthofltthtotho unwwwommmmumummwm woman. ' mmmmmmmauwbymmuon dotoohovodthotoothoolootronocouvityotthonmuthoficeimr otrootorolnoroooodthomototop, hambuo mun..- tova‘od "or tho fourth otop, hos-aw dloo’oolotloo. filo, tho tonic muumuuwbymmuummm «MammmomWommMo-t .mootmunaoommmmmqu «Mom—unantlootmuddoohdnbmuoo. tho ooultootthouomonottolnmmmwuthomum amounnthopoodnmohtomdmodotwmmlyby tho routs." toudoooy of tho H-bronoonldo to undone hotorolnn or wwwuuumwwmnutmzmmn much-antenna... fhotondmtoondormhotmlmoor hooolruo tum “I worn“! by tho olootmogotiflty of tho Cuba otitoootouthooddoottoohodtothooubowlum. mowummmmmm°c.uao°o.m «mummunaommmum. rhoootoot‘ tnoudtodmotlmnmuonqluorouodbyuimooooot mm. nommwommumu-mcmmum 82 uthtnorooodngtounpmtm‘o don-outrun! thoduolnotnroottho nonunion. Bodymmhoninmorooponoiblo forthobronimtian motion tho rotio 0: “do chin to ring broninntion would not chomp uthoobongointmorohro. Bronino roootod nth toluono at We . ond u 80% . WW byorroorodieolmm. Mon-omwbythohichutioot momummmmmounmnmonuoor unamumbrmmbmmoumm. Tho roto determining otop in tho ionic bronimtion mud oppoor to ho tho mun hotorola'tia :11.th of tho nits-03oz: bro-an. bond. Thorntodotmngotopnthormodmnmmd Wuhan-mummummmumumm Mann-bond. Hm,thoro1ootthomoom1¢1omtyot attain. oopooumomcoonohorolotfiolyhrgouoonotm Warmndhthomanm. Itunotmwothoo thobmnimeonplaloodotouuuoidoohoubmtun. Itto mmmothortmmoaqloxtoomtowtottho mmwwothuitummmoprtorthotmomdndim nah-mm. Thohrudnoiolooulqboundmthooomluomoolt eon ho roodny WWW «mum. ThoroutionothydrogonhroddouththoH-hronouidomu- chdod in tho whom:- boon” or tho poooibmty of tho rotation of froo or Wbm. formed during tho nation of tho l-bromomido with tom, giving Ivdrogon branch. Tho account notch]. bolanoo obtainod in tho vocation at 80°C. mindo my loos or bro-mo in tho for: o: hydro“ mudo. 8.3 A kinotio imootigation would greatly help in on mowing of tho radical mhanin. Tho roonlto ot thio work aro not conploto onough to allow for any ”oping gonoraliaatimo. It mid ho outpoctod m- the infrared data that tho ll-bromoaootmido mid givo tho motoot amount of oido chain broudnation and that l-bmmtriflnormotaMdo would givo tho amalloot amount or aide chain bronination. Tho roportod (6?) rod action: otthoootvoroagmtouthtohanotmdtooupportthio prodiction. rho oomlation batman tho intrarod data and tho method or aimoiation of tho anti-om broad.» bond «no to hold for tho l-hrouoo mdoo. Humor, itiomtknomu’thioomotochniqnooonldbo 1W nth tho H-bronoinidoo. Subotamoo liko lcbrommccinimido and l,l'-dibronodinofl1y1hydantoin aro good radical hmting agent” hooroao, I-bromghtarinido and l-brmhmhydrophthaliuido aro not oo good. Quitopoodblythobroninooonploxplmamor roloin tho nation and ohould ho thomgfl: invootigotod. WEREEHAL A: m:— 'I , ‘: W rho ohlorotoro oolvont woo uohod with matrotod mic acid n 50%. thou oith «manna um, row by diving on;- «1m chlorido, attor men it on W. Carbon totroohlorido too uohod oncooooivoly with 10 pour out potooom rum-moo «lotion, oomontrotod oulfhrio ooid no! mun: tutor. It no thou driod our calcium ohlorido and diotillod. Wummmummmmnmnw an aqnoouo tormo mitoto oohtion and Woo ao noodod. ’l'rinooo-ooootio ooid no diotillod Iron 25 x. or phoophomo pontoxidouoingaBOu.hy2oa.horooo1mpookodw1th glauholiooo. Toluono no driod ovu- oaloiu chlorido and diotillod oo noodod. rho H-hronoaaidoo and iridoo woo-o roorntalliood tron oorbon totro— Mo and their purity dotorninod iodinotdoony. rho ooltingpointowco dotoroinodooing oapiflorytuhooina “no” on both and mo W. m- P $ (68) Intoatnlituthroonookmndbottounookwooplaoodfilé 3., 2.0 who, ot phoophorono tribronido. Lt roan Wotan, 320 3., 2.0101“, ornquidhrmuoaddodolomovoropmodoftm houro. A yollow oolid. phoophorouo pontobrouido formed. Thou ono 11w of motrioal totrochloroothono III addod mum by 2115 3., 2.5 noioo, of amnion bromido. “rho roootion nixtm-o no thou hootod at ito roan: tomporotnro for unity-{our honro ot mini-a point no tor-tho: ovolntion of hydrogoh hromido took plaoo. Soon amounto of hrodnoworooddodporiodioanytoroplooothotlootmoto diooooi- ation of tho phoophorooo pontohronido. Tho oolvont woo than rmod by diotinotion lowing a oryotollino ohm which on rooryotaniootion tron honoono govo a whito oryotonino oolid. Thio phoophonitrnio bronioo io roportod (69) to ho o nixturo of tho trioor and tho totramor. Bowovor, for tho pox-pom of thio invootigotion tho ooporotion of tho ioommuodoonodmooom. Thowoight otporophoophonitrilio hronido no 1615 1., 0.8 who, a yiold of ho por oont boood on tho mount of phoophorouo tribronido hood. Tho ootoriol loltod ot 192-193°c. Tho W mung point (69) for on. trinor 1. 191°C. and to: tho um 201°C. (69). Tho roaotiono twolvod aro mounted by tho M oquotionoc P33, ’ h. -’ PB!" Para 0 lm‘Br—ov pm. 0 mm: W (7°) Intoaouolitcthroonooknooknttodfithootirm,po1n1ot mmmwmplud 20qu 33o? ‘o’ 0.25 ”1“. am “Mould 600-1., 5.75391“, otmdronootmnhor. 86 Amazon goo woo than bubbled into the ohovo cooled, otirrod, reaction oolution at o rato or 900 to 1000 ml. per mmto. The motion, ao it proooodod, wont throng: a color ohongo from yellow to brown and find]: to orange at tho o-omplotion of tho motion. Tho roaotion no completed in two houro, after which tho reaction oixturo no oat ooido overnight. in orange oolid ooparotod from tho oolntion mioh itoolf m a bright rod color. rho oolid who ooparotod 15w filtration and than ooctrootod with oovorol portiono or anhydrono ethyl othor. Tho othor «tract as allowed to ovaporato at roan tomorotnro leaving a oolid rooiduo of orange cryotalo with a choraotoo'iotio odor. Tho pure nitrogm mlfido weighed 1.5 3., 0.006 mloo, which in o 20 per cent yiold booed on tho amount of mmr nonoohlorido toad. rho mtoriol mm at 177.178°c. no reported (70) halting point io 175°C. ' Tho roactiono involved oro roprooontod by tho “Mg equation: 162m, 9 63.01.-12mm o 33‘ .33 This proporotion woo ropoatod oovoral tiooo to obtain omngh otorting material for tho oynthooio or nitrogon cuticle tornado. am on o; a 21mm M do would... Im (71) Intooonohtcthmnookflaflflttoddthootirzor,“ whom no a dropping tonal woo-o plaood 16.35 to, 0.09 noloo. o! nitrogon ultido and 500 I]... 5.! noloo, o! roagont grado carbon totroomorido. to tho otirrod ma, kopt at 3.0%.. 32.0 g... 87 0.2 310108, or liquid bromino was aided dropwiso over a period of two hours. Tho reaction nixturo m otirred for on odditioml clover; hoor- ot 1.0%. ond then filtered to removo any unroactod nitmgon oulfldo. Tho filtrato m evaporatod by mono or on upirator and on careful hosting to roamo tho loot truce- of oolvont yielded o bromo colored mrphouo oolid. No physical oonotanto could bo found in tho litmturo for tho nitrogen sulfido broad”. However, tho bronoo color correspondo to that which hon boon roportod (72) for nitrogen luli'ido totrohroaido. The bran" Iolid obtoinod by tho obovo proood'uro liberated bromine at temperatures above 150°C . to giro a white amorphm ”no which did not melt ot temperatures up to 230°C. Tho weight of tho above Intern]. In: 23.2 3., 0.055 moles, vhioh is o. yield of 62 per cent based on tho amount of nitmgon sulfide need and tho mtion that tho compound famed in tho nitrogen 011151ch totrabrmo. 12o Emlyn gt ghmmw Brows 3th mlohoxono Intoohdllita,twnooknuktittodoithootirrorwo roflmc oondm taro phood 20.5 3., 0.1 molo, a Whine broado mi 75 I]... 0.78 solo, at roogont grodo oubon totroohlorido. To this otirrod fixture, hootod on o otoon both, In «Mod 50 to)... 0.1.13 nolo, or oyolohuono wish had Jolt boon tubal with oqnoou torm- oultotoondtroohlydiotillod. rho otirrodroootionuixturo Ilu hootod ot ito "flux Wotan on tho Itmhoth for throo honro, mmiohtuothoromnoovidmoozhydmgonhrmdo being formed. The carbon totraohlorido and exoooo oyolohoxono were removed by dintillotion at atmospheric promo lowing a mite cryotallino oolid. The oolid was dried under vacuum, and on being oat ooido overnight it turned unmet black. Go rooryttolliution from carbon tetrachloride tho black solid gavo to» COM, one of which on pure phosphonitrilio bromido which had o melting point of ion-195%. Ito reported (5;) melting point is 191%. for the trimor and 201°C. for tho totramo . Tim second black solid was of unknown composition and on: not melt at tower-ammo up to 230°C. The reaction botwoon phoSpEmnitrilio bromide and cyclohmono no ropoatoc‘i. In tho some apparatus an dowri‘ood abovo were placod 9.2 3., 0.025 molo, or phosphonitrilio broooido and 63 51., 0.67 mole, of oyolohoocono mioh had boon {roomy purified by washing with W formula mlfoto and distilling. This reaction differed from tho one pronoun: doooribod in that no carbon tetrachloride no uood oo o oolvout. tho heterogeneous mixturo woo otirrod and hootod on tho otoon bath for {our homo, during uhioh time not all of tho phoopho- uitrilio bromide: roootod. Tho roootion mixture no filtorod and the com II-IhOd with carbon tetrachloride. The moon totruhlorido oohtion no Mined nth tho original filtroto. Tho oolid one boing dried wifizod 7.1; 3., 0.036 molo, and represented 80 per court at tho Cutting motoriol phosphonitrilio bromido as judged. by o. mod nolting point, 192493°C., with on wthmtio sample of phosphouitrflio bmddo. Tho combined filtroto and carbon totroohlorido oolution m eiotilled at atmospheric preemro to remove the carbon tetra» chloride and oxoooo oyolohueno. When the toiling point reached 83°C. o violent decomeition took place. At the time of the decomposition there woo opproximtoly 30 m1. of o yellow liquid in the distilling flak. After the decompooition only o block non-ooMotiblo oolid remained. bio utiofootory oxplonotion for thio deoomooitim con be offered at the present time. 1» R maiflimgg smogmbrmofieooowm Intooholxlitor, tmnoekflukrittedwithootirrerond reflux eondm were ploced 1.6.5 3., 0.09 mole, of nitrogen mlflde tetrohromido on! 15 I]... 0.78 mole, of reagent credo oer-hm tattoo- ohloride. Thio mixture no otirrod mo then brought to ito reflux toaporoturo on o oteon both ot which point 1.1.1 3., 0.5 mole, of mlohueno, which bod Juot previously been fished with aqueous term nuoto end distilled, m oddod. The reaction m'm booted It ito reflux teperoturn for six houro and then allowed to cool to room mom; fixer-upon, o dork brown oolid‘ oepu'otod mm the reaction mixture. The oolid woo removed by filtrotion one ooohed with meal portion or oold eon-ban tetrachloride and theee veto comined oith the original filtrate. The solid, mounting to 9.5 3., did not molt ot taporotoroo up to 250%. am on not identified. The «mixed tiltnto one cox-hon totroohlorioe mhingo were distilled ot otaoo- phorie prooooro to we the eorbon tetrachloride ond access cyclohexene. Tho miduol liquid m froctionelly distilled moo:- voomm. ho grams of o pole yellov liquid, 13.13. 69-7290./ 13 m., and 10.0 g. or o yellow liquid, b.p. 99-101°c.m 390., were obtained. The first fraction gave o pooitivo test with olcoholic silver nitrate oolution, Meeting on ollylic bromine atom and gave on positive teat nth memo pcteeoinm pommto ocluticn which incliooteo on unea‘hueted compound. The refroctivo index of the com- .0 pound on “D 1.5235 Imich 1o comparable to the refractive index, oc , 11, 1.5230, reported (73) for 3-bromoqrclohmcone. The second fraction 0 turned bleak when exposed to moist air. This darkerdng property of the oeoond {motion and its boiling point, 99-101°C./13 mm, are identical to the properties reported (73;) for 1,2—dibromocyolohcxeno. Intooholtlitor,ononocktlook£ittedtlthoro1hxomdonoer were placed 17.8 3., 0.1 mlo, of Nehru-emanation 125 ll., 1.55 neloo, of amoroforo one 3.1.1 5., 0.5 mole, of eyelnhexonowich bod mmmoddthoqumtm ooltotoolddiomlod. mmmmmuiunmwmtm whinflehunothom‘omlotooombytho obmcooi’mcolormrutioninthoroocticnmmw Iithonmttorohompctuoiuniodidooolotion. Maconngtho roootion mixture in on ice both o oolid precipitated from ”lotion fidehmrmedbyflltnticnonddriodundnvm Mouton-in weighed 5.0 3., 0.05 mole, end had omed melting point e: 12h«126°0. 91 mmuummudomu idmtieolodththonoltimpoint o: the letter ohm pure. Tho tiltroto no diotillod at otaecepheric We to two the oxoooo chloroform end oyolchenne. Attempted mum; diotillotion or the noioeol liquid under mm reoulted only in doccwooition and no identifiable yroducto were isolated. own-ant]: on]: him boiling notoriolo m want. This reaction ”repeated fourtimondinnocooodiduvollfiiobroninotiom We The Reactio- of Rnéz‘ogoosuccinisoifio with Cyclol-sofi'mo in Forbcn Tetra- gmriég W w T w, w Intootmlflitar, tmnooktleekfittodtdthootirrerond reflux condenoer we placed 17.8 3., 0.1 solo, e: l-hommccimdo, Hal 3., 0.5 mole, of cyclohoxono one 73 IL, 1.2 noloo, o: corbm Mnohlorido. The nation mixture no otirrod and booted ot ito reflux Where for on 1101).? end o bolt, in witch use the rmtion uooomletoooindiootodoythooboomootooolottoruticooithon m otorch omd pctaeoiun iodide solution. The end of the mention "Mindleotodbythoproeemootooolid fleetingontcpef tho roootion «lotion. the reaction mixture to cooled in on ice hothondthoomtorodtomthomtooolidmchotmmg under noun melted at 125-126°C., the me oo mcininido. the moinizmio weighed 9.1; ¢., 0.095 mole, reprooenting o 95 W out recovery of thio byprochmt. The tiltroto one distilled ot atmospheric preoooro to we noon cyclohoxenc no carbon tetrachloride. Thoroddoolliquiduothondfltfllodundcrvooomtoyieldoyolloo 92 liquid with o boiling point a: 69-72°c./n m. It at" o punitive toot 81th an alcoholic oilvor nitroto solution indicating an allylio W oton and also me o positive toot for maturation with a ”lotion of bronim in carbon tetrachloride. Ito refractive infiox III or 1.5233 which is quite camels]: to tho refractive index, n? 1.5230 reported (73) for 3-bromooyclohmzono. This product weiggmig 10.1 g., 0.63 solo, represented o 63 par cont yield of 3-bromooyclo- buxom booed on the amt of fl-brommoizfimido used. A block tarry residue weighing 3.5 g. mainod after tho distillation. The Reaction of mm J‘ibf'omgiimot'ym'fiantoin with leohoxena in orofiam Into C hi1! 11W, one nook flu}: fittod with o reflux condenser ion placed 1'30 ml... 1.65 min, of chloroform and 1.1.1 3., 0.5 mole, of cyclohoocono which had just previously been distilled after washing oith oquoouo ferrous mlfoto. To this oolution no added 28.6 3., 0.5 mole, of 1,!“ kedbmdimatwngfiantoin. in uothomio reaction lit in libcroting Efficient heat to the reaction minors to hoot it to it. reflux tmnturo in five mirmteo. At the and of twenty limit“ tho reaction mixture had stopped refluxing and o homagonool lolntion resulted, at which point tho reaction no not complete oo indicated by tho development of o black color whom 3 drop of tho motion solution was tostod. with o starch iodide solution. Exterml host to! then applied to bring tho reaction solution to its reflux impel-3mm, at which temperature it was kept for an hour and a halt to (:0an the reaction. Tho apparatus mo immediately arranged u'; " -- 93 for distillation end none of the ozone oyolohomom end chloroform mo distilled et etmophorio memo. The reeiduel liquid me than ooolod in on ice both end e lolid eoperetod from solution Ihioh no recovered by filtration, end after drying \mdor room had a melting point or 172—172.°c. the melting point or. pnre dinethyl- hydontoin ie reported (75) to be 175%. on. Iolid Ieigtxod 8.6 5., 0.07 mole. ohich m e. 68 per cent recovery or thin bymdnot. ittmptod dietilhtion or the filtrate undo:- voonnn mood extensive dooonmoition "outing in e block vieoooe nee iron which no identio tioble notoriel could be iooloted. Tho Reaction of N.R'-gbmmdimotgzlm toin V139. mlohoxono in Witnchlorido Intoeholi’liter,twneok!luktittoduitheetimrendo reflux condonoor wore placed 11;.) 3., 0.05 sole, of Hm'cdibronoo dinothylhydentoin and 75 n1., 1.2 noloo, or carbon tetrachloride. To thie ttirrod minim m edded hl.l 3., 0.5 mole, o: oyolohoxm uhioh bod boon from]: dietillod otter first being uehod with mom form ”note. The rotation mixture In heated at it. reflux tempereture for one hour, ot which tino it gave e negative teet lith «new etorch nod poteeeinn iodide eolntion. “rho reaction mixture melloudtooooltorooumeroturoendthe eolidmiohooponted tron eolution no recovered by filtration and otter drying under nam- hed e melting point of 172-17u°c. on reported (75) melting point for pure mm is 175%. the night of this 9h byproduct ‘8 5.5 3., 0.01. min, onion one en 85 per «at room of tho dimmtoin. The filtrate one dietillod at ehoophorio We to woo the mm oyowzuono end outo'n tetrachloride, loathe roudoelnmidmflxmmetillodnndorvmtoyieldo yello' liquid mien bed a hp. 69-?2°6./l3 m. Thie ntcinl me a punitive toot for ellylio breaine with en alcoholic ulvor nitrote oolution on! e poeitive test for Motion nth equeooe poteeeinn permngenete eolntion. n hed e roman index a: of 1.5239. to. ten-eon" indm reported (73) for we JWohume ie “Dec 1.5230. The night of tho 3~brooooyolohemo an 8.9 3., 0.06 nole, mohoorreepometoeyieMoISSPfl'oont. Amount-aim MLO pruninedinthedietilletimeqnipent. mum of HEWEwon g the Dark. (67) Intooonelitor, twoooki‘looktittoduitheoondmorond etirm more ploood 200 ml. of anhydroue trifluoroeootio eoid end 23.0 3., 0.1 mole, or olive: oxide. Thie mixture no ooolod eligmtly endetirreduntilollottheeilmoxidohodreootod. Thonetroou Wotan 18.7 3., 0.2 mole, of mohlorooootomide one eddod in eevu-olportione, tboleetofiziohmrineeointothenuktdth SOnl.otenhyoronet1-iflnoroooetioeoid. thienixtnreueeurred for one hour. Than 32 3., 0.2 nole, of chilled hm diuolved in ‘The reeotion {look In covered with e beg node from ngxtproot block popu- need to protect photopephio pope". During dietilletim ondothor Wont-innipuletionetheqpermmeinhrly protected ogeinlt light. v— ‘«- 95 5031.0d‘emydrmtr1flnmeeetioecidmeddeddropuaemre tee hour period. rho mum: mm m Itirred for en edditimel hour etter the addition or the bromine m eomplete. The reection mixturemthmmteredtorewvetheeiherhrontdemiehm “shed with three 25 :1. portions of chilled, «mam tritium- acetic «id. The mmu and week eolutim vere nominee! end die- tilledetrnomtwpuemreendepreematmnn. mamma- weticmidefimmbrodmmocollmtedinehrxetnpmch newledinedryiceemmlemmlbeth. mmdthe trinmuecetieecidendbroninemmedeymulm. mmemimedietelydeereeeedtel.-.tormerelme muonhreyelloeeryetemneeoudeulett. “Rotunda eerner preperetiene of l-breeouonoohlomeoetuue that 1: the mulmmmdeetrmwrtwmmm dwmeitimtockplueendfheyieldetpromumw. Freeing eithuyellevoueleet‘euedtepnducemle. mommndruiduoummunuumumm tetrwhlorideinthemktogivem.03., 0.12mi“, expel-elm- mhhmeeetenide met: me e halting point a: tin-71.5%. The mung pom reported (67) tormecowoundie‘lsoc. Theyield of theprodnflmSBperMMmmmtotmwMe and. mmmrotmmmmdmbyenm amotthepereentdbmutheeow. Itne found thet the solid bed 1.6.36 per cent bred». The eelmleted value 1e 1.6.31 per cent Mom. Into e one liter, two neck flask fitted with e oomimeer and stirrer we placed 200 ml. or ufixyfirooe Moroccan acid and 23.0 3., 0.1 mole, of silver oxide. This misture no heated gently and dined until e homogeneous oolution resulted which required general]: free e half hour to en hour. Then at room tenperetxxre 25.6 g., 0.2 mole, of dictfloroeoetmide we edded to the above mixture in eaverel portione, the loot of this}: no rineod into the reaction {leek with 50 m1. of trifluoroacetio acid, eftm' which the mixture In I stirred for en hour at more taper-ohm. Then 32 3., 0.2 mole, of . chilled hm dieeolved in 50 ml. of anhydrous triflooroeootio eoid were edded dropwiee over e two hour period. The roeotioa mixture wee etirred for one hour alter the addition or brownie one complete. The reaction mixture no then filtered to rm" the oilver bromide wiohmmhoduithflmeezsnl.portioneo£omned. enhydron. trifluoroeeetio acid. The filtrate end mh eolutione were combined mothendietilledetroontemperetoreondepremreormm. The ezeeu bromine and the trithoroooetio eoid we collected in e urge trap think: one eooled in e dry ice end ieoprowl eloohol both. to the eolvent one being romved e shite eolid elouly eepereted from the reaction ”lotion. when approadnetehr threeoi‘wrthe or the eolvent had beat removed the dietilletion no stopped end the eolid we eeporoted by filtretion. Thie eolid on dried under vacuum end recryltellieed from carbon tetrechloride to give e product in the 97 tom of white needles which had e melting point of gas-95.3%. The mlting point reported (67) for H~bromodichloroaoetaznide 1: 96°C. Complete removal or the eolvent from the filtrate at room temperature am e preeme of 10 m. we e yellow solid residue. This residue on recrystallisation from carbon tetrachloride gave a colorless product in the torn of neodloo which had e melting point of 93.95.5°C. The ‘ combined eolide, pore l-bromodichloroecetmdde, which weighed 33.5 3., 0.16 mole, represented on 81 per cent yield booed on the amt of dichloroooetemide used. The bromine context determined for this material was 38.66 per cent. The calculated bromine content of Mmdiehloroeoetmide is 38.63 per cent. tion or ii eoetenide the Dark tom eoneliter, mm}: mntwuthneomW-m otirrer wee pleced 200 ll. of. enhydrooe trinooroeoetieecid end 23.0 g., 0.1 mole, of eilver oxide. Thie eixtore we cooled elightly end ‘etirred mtil e homogeneone eolntion reenlted. Thie general: required e half hour to en hour. Then et roan tempereture 32.0 3., 0.! mole, of triohloroeoetenide we eddod in eererel portion, the loot or which we rineed into the reeetim {leek Iith 50 ll. of trineoroeoetic ecid. Melittoreneetirredrorenehoor, etrooetweretore, etterthe addition of the with no muted. Thu: 32 p, 0.2 eole, of chilled bro-inc die-elm in 50 ml. of more“ triflooroeoetie eoid are eddeddropuuovereteohoor-period. Thereeotionnixtoremotirred for one hour after the addition of the bromine one cowlete. the reeotion 98 mixture was then filtered to romovo the silver bromide which was washed with three 25’ ml. portions of chilloé, mfiyirous trifluoro- lootio mid. The filtrate and as}: solutions were combined and then distilled at room temperature and a pressure of 13 m. 'i'he triflooro- acetic acid and excess bro-mine were colloctod in a. large trap which was cooled in a dry ice and impropyl alcohol bath. is the aolvont no being rammed a white solid slowly separated from tho reaction ”lotion. khan approximately two tl'dl'do of the solvent 1133 been removed the distillation m stappod and the solid was separated by tiltntion. This solid was dried under vacuum and recrystallized from carbon tetrachloride to give 3 white crystalline product in tho tom of needle: mulch had a melting point of 11313-123500. The melting point reported (67) for H—bromotriohloroncotamifio 1: 125°C. Completo removal of the oolvont from the filtrato at room temperature and 10 m. pronoun gave a yellow colored solid residue. Thin residue was mmtallinod from carbon totmchloriaio to give a colorless crystalline product in the tom of noodles which had e melting point or 123-123.§°c. Tho combined Iona, pure R-bromotriohloroacotamiéo, which weighed 33.5 3., 0.16 mole, represented an 80 per cent yield based on the wt of triohloroacotmido mod . The bromine content determined for this material an 33 .11 per cent. The calculated bromine contont in 33.12 per cont. 99 on of H-Brgmetfiommootofldo in the “ark Into In em liter, two nook flask fittod with a comionsor and stirrer wore placed 230 m1. of uni-aromas trifluoroacotio acid and 23.0 3., 0.1 mole, of silver oxido. This mixture mo cooled slightly and stirred until a homagenoous solution rooultod. This required ono hour. Then at room tarporaturo 20.5 3., 0.2 mole, 1‘ ethmootofldo was added in several portions, the lost of which was rinse-:1 into tho reaction flask with SO :51. of ardiydrous trifluoroacotio acid. This nurture was stirred for one hour at room tovporaturo. Then 32 g. , 0.2 mole, of chilled bromine dissolved in 530 ml. of maydrouo trifluom- acetic acid were added dropvise over 3 two hour period. The reaction nature was stirred for one hour after tho addition of the bromin- nolution was complete. Tho roaction solution ma a vory dark red in color at. this point, and it appeared as though a considoreblo amount of the bromine had not. reactod. Tho reaction mixture woo thorn filmed to remove the silver bromide which was washod with throo 25’ ml. portion. of chilled, anhydrous trifluorcacotic acid. Tho filtrate and wash aolutiono were combined and than distilled at room temporaturo and 10 mm. proasuro. Tho trifluoroaootic acid and moon: bromine woro collected in a largo trap which was cooled in a dry ice and ioopmpyl alcohol both. This prooodure failod to oauao any insoluble material to separate from the reaction mixture. The distillation us than confirm-oi at 1 am. pressure for a half day 1821c}: gave only an oily residue. no residual oil was takon up in carbon tetrachloride, but ‘3. .._ w ’4... - _..3_ 1.! -_:' .13 I’M Attofl ted firm ' ation of fi:hgmot§zoqaoot&fldg;g the For}: Into a one liter, tvo nook flask fittod with a oozflonoer and stirrer wore plaood .200 ml. of moi-animus trifluoroacotio acid. and 23.0 3., 0.1 mole, of silver oxide. This mixture was cooled olightly and stirred until a homogeneous solution rosultod. Thio required ono hour. Then at room mporaturo 20.6 53., 0.2 mole, of ethoaqraootouddo was added- in oaveral portions, the lost of which was rinsed into tho reaction flask with 20 ml. of muiydrous trii‘luoroacotio acid. This mixture was stirred for on. hour at room tomoraturo. Then 32 3., 0.2 mole, of chilled bromine disoolvod in 50 ml. of ammmus trifluorou acetic acid wore added dropwiso over a two hour period. The reaction mixture m stirred for ouo hour aftor tho addition of tho bromine solution was couplets. The roaotion solution was I very dark red in color at this point, and it appeared on though a oonaidoroble mom of the bromine had not reactod. The reaction mimuro was thou filtered to move the silver bromide which was washed with than 25 ml. portions 01’ chilled, onlvdroua trifluoroaootio acid. Tho filtrate and wash solutions we combined and than distilled at room temperature and 10 m. proosuro. Tho trifluoroaootio acid and excess broudno were collected in a large trap which no coolod in a dry ice md isoprOpyl alcohol both. this procoduro failed to owns my molublo material to separate from the reaction mixture. The distillation no thou contimod at l no. pressure for a half day mien gave only an oily residue. The residual oil was taken: up in carbon tetrachloride, but 191 colored solution the: pressure hogan to rise slowly to 30 m. and the solution tuned a dark red color. It apparent as thoug‘: some decomposition was taking placo. 'fiis dork rod oil was form! to con- tain only a trace of active brownie and was disowdcd. Mica Raw“ The oodium hydroxide solution coed in thin uork m standardized against potauiun acid phthalato. The hydrochloric acid Iolution ulcd in thin work in Wired against a otandard Iolntion of acdiun hydration. The ltmdn‘d codiun chlorido caution and in this work was pro- parad by 1131ng a ample of Baker analytical grade codium chlorido, dimlving it in distilled rota and diluting to the proper volume in a calibrated volumtric flask. The ailvor nitrate tolution used in this work was ataxia-diced against a standard ”diam chlorid- solution. The Iodiun Wallets coluticn used in this work was atmdardiaod againat'a weighed «ample a: potassium bromatc. Magi fimcodurog Iodine-trio Katha-d for t’co Fotmingjfign of Acti*..'cj3rofi_no in li-F’romo- £13166: wand 1. dos W" W ' V " _, _ Into a on. W litcr iodination flank were placed 5 ml. of gloom-cutie acidand6031. ofafrumyprcpmdhporcant moons “lotion or potassium iodide. Ln accurately weighed couple of the Woo or mm was than added to the ioéhmticn flack 1432 and tho Em: romuim particlos of sac-42M wore 113.31sz into tho flask with $339 10 ml. portion of potassium iocico solution. Tho neck of the iodinatiou flask was than waclzcd with a. for ml. of the potassium 10:16-53 solution. The 11.3. was stoworcc‘. and a few drop-s of the potassium iodide Isolation mm placed cram-i the edge a: the stopper. Tho flask was man catc'tcu until all of the E-broaoamicc or imico lad dissolved. The stopper tar-.5 rozrzcvcd and the mils or the flask were WES dorm with a fine stream of water from a wash bottle. T.zc solution one then titrated to c starch cnd~point with a vagilwd 0.3.}! moi.» thiosuli'ato solution. To ccrr act for any 023ch due to immiticain the. glacial acetic acid or potaccium iodide, a blank dotcmfizzation m We in exactly the was eypcria'aontal procodm‘a but without adéori H~brozcounide or inside. Result: wore calculated using t: o forzmh, 7.992 x 311.8 30 : at 301‘!“th 5203 . pm- c-nt not 1"3 hm. 2 a: It. 3331910 mist-ital Techni cud-a 1*‘F‘www‘io~v«v’* to Moccnt for All of tF-e emrigc in the Reaction Between t‘Xc N-fircmoaucc and Toluano The reaction, in the abumo 0: light, bbotwaen the fl-brcmcmidu and tolmc at Mafia. m ccrriod to emetic: a mm.“ by the absence of a color famticn when a drop of tho reaction mixture .1 Aw“ M 51‘» thermostatic bath and roaction flask wore protoctao ago... .nst light byccvaring tho apparatus with lightyrocf black cloth. 1C3 taste-.3. with an aquaois starch and potassium iodide solution. The reaction flask was tho-n ot-omzorec‘v, coolod in the refrigarator for several hours, and. filtorocl through a bust-nor Emma-l to rmmvo tie white precipitate. To insure agaiizst poss"~lo 1:2.ch loss the filter flask was cooled in a dry ice and iocpropyl alcohol both and an aciditiomal trap, cooled in the sax-29 way, was plaza "1c. botm on the filter fleas; and the asxdrator. The solid '55 xmshod twice w’th chill-ed carbon tetrachloride. The filtrate) and cog-Joined makings were dis- tilled at atmospheric pressure to remove completely tho carbon tetra- cbloriio am mat of the moose toluene. Tho rosidual solution nozmining in tho distillation £1331: was cooled and 2:: ml. of boozy}. alcohol is added, to servo as a chaser Ming; the distillation of the monobrozinzzt-ad toluenos. The solution was then vacuum diotillod usmg a 30 cm. via-row: colum fitted with a distillation howl. Th material boiling at temperatures up to 93°C./10 3:11., the boiling point of bomb-*1 alcohol, was ci‘..llccted in I weighed receiver. The; ciistilL'Ltion was steppe-2d when a. drop from the @11va tip of m tasting-um head gavo no precipitate-t with an alcoholic silver nitrate solo ion. Weighed samples were tel-on from tho weighed istil'iato and weighed rooiduo of the distillo‘ion for anagram for total imlogen, active 7323.0an and mid-e. Total PmEQ (76) , Sample. of the distillate mifizing approfimtely 1 g. nod ample. or: the residual collation from the distillation weighing approximately 101; 2 g. war. rinsed inta a quart” litm- flat bottom flasks with 25 ml. of 99 per cent isoprOpyl alcohol. Two arm of Indium metal, out. intoeightpiocaamwdodmdthemmkopt Justus.“ reflux tag-1mm. for three hours. Eamon oodimn met-.1 m destroyed by udding water dropwlu throng: the mm. A 50 :1. may of water was aided to the Donation and after cooling it n. neutnlined to a phumlphtlulain and point nth GK nitric acid followed by titration with standard 0.18 :11":- nitrato caution. Benin u. used :- tha indicator and 10 131. of a 2 per cent dextrin Caution m tdciod to keep the cilvar humid. precipitate in I colloidal Wen, than affording a dump and point. The volum multiplied by the mmlity of the standard silver nitrate solution gave the total minor of mini-- oquivalents Of bromide in tin sample. Active £31333 ‘03": 3.351 Q30 3.14:3 Samples of the cistillata, waging a; 930......th _; 3., 33: 3 rinsed with 25' ml. of 5’? per cent isepropyl alcchcl int 0 qua-ray lit3. , flat bottoa 113.333. A 50 3:3... quzmtity of Iii 50313.33 2.3123333} sclufiion an added and um solution was 1:3pt at. its reflux ’63: {33.32.3319 for two hours, aftm" which it was 330136. am‘. neutralizcd with (a: nitric acid to a manolpl'stlxalcin and point. Following this tho solution was titrated with :3“me 0.111 silver nitrate to an 3333.11 midpoint. T‘se volume miltiplieci by the nommlity of the $931le 83.3. ar :13." ‘ats Ovulation gave the amber of miliequivalents of active bromine in the maple . 105 do ‘I’no necesaiw of analyzing the mops-rated amide m determined by the nature of: m mo. That. is, any unupmtod amides contain- 111;; ‘nalogm, mob in memos-mamas, muld certainly be round in the) residue of the 6101311181310!) Ind pow}: in tho “mat... Duo to tho nature of tho mm: mm in analysing tor total and octiw maggots, the pram. of ohloroundeo would affect tho results of the total halogen; and ponibly the can" bologna. Tm, by detox-aim the Mt of magnum amid. a correction could be me for tho halogen in the waldo. when no halogen in. W in the mid. nah o damnation m not mom. 33mph: of tho distillate weighing W139]: 3 g. and 3333913: of the residue from the distillttion weighing IWW S a. mo rinsed into separate one quarter 11W {11% button MI with 25 ml. of 99 par cent isopropyl alcohol. m3 flock to. set up for distill:- htion in such a manner that tho delivery tuba of the dtotilh‘bion hood axtemled beneath the surface of 1 50 ml. (enmity of freshly wowed, 31711133, four per cam, borio acid column: contain“! in the receiver flask. Fifty ml.- of. n 0.53: ”dim mama. solution uh added to the distilling flux anti the solutioa in: distilled for one half hour . The b01313 acid oolution oontdning the flotilla.“ and I. blank borio acid solution mo than timed with standard 0.02m hydrochlo r10 acid solution. The indicator Elation m u freshly med mixture of mthyl red. and mundane blue in a ton to one um. The first appearance of a red color was taken as the and point. 105 Tho diftoromo in tho volnmo of tho W monohlorio ocid solu- tionroquirodtormobhnk maths mumthovolumo ofotandard mid roquirod to mtroliao tho ammonia produced by WW3 or the wide. Tho volmno mltipliod by tho norzmlity of tho otmdard hyvlro- ohlorio ocid solution mo the W of nillioqnivolonto of mnia from the mido. A mum of. tho tumor 01’ mlioquivolonto of ammonia mm, comm to the Maze of halogens in the wide, no tho correction applied for the halogen of tho omido. Fox-mun, no unido not found in tho 41-min. Ind, warden, no carnation to: wtivo wagon had to be oppliod in thio mo. Tho mm of mid: found in the residue was mod on o mtion for tho total halogen. The motion, in the absence of light, bow“ tho NW3“ ond tolumo at 30.0%. mm mm to proceed tor mwmr noun, ot mien point tho motion on 31m incomloto. The reaction colu- tion at thi- tim no colored 3 dark red and m imodiotely wrapped in block photographic: paper and cooled in the refrigerator for moral houro. Tho oolid woo separated by filtration in the dark into o filter flask connected to o trap cooled in an impropyl alcohol and dry ice hath no described previously. The solid ms dried for two houro in this W and. then transferred: to 4:. half liter volumtric nook where if. was partially dissolved by filling the flask to the proper volmm with when totrwkflorido . The insoluble mtoriol no the amide which has a low solubility in tho solven . The 11:33th l-bromoamfia totally ciissolvod in tho carbon tetrachlorim and the 10? romltont solution had on orange rod color. An aliquot of thin oom- tion no Mon 11th 5 ml. of glacial acetic sold and 100 3.33.. of a {roomy propane: tour per cent potassium loci-1d. oolution. The 1115093th 10am: m titrated Iith standard 0.2x loom thiosuliato solution m from tho volnno of tho latter solution not! tho mount of mated H-brotnouddo oould be ooloulotod. An dtmtlvo method for dotomlnlng tho. want of unroootod ammo. m to dry and we: on. original prooipltoto a: mac. Moundmthmgroondmdomploomomu,mdthomtot urn-mud Woo woo detox-mod lodimotrloom u outlined ohm. Mo mthod, however, no mt u reliablo‘ u tho ono pmiouoly described. Tho filtrate from tho Woo toluene reaction mixture no almodork rodoolor. Ituoooboorvodlnthooarliormpomoonto that will thin oolution was being flotilla: to remove tho urban totrmhlorldo ond noon tolnm tho dark rod color disappeared and m of Mongols brooddo mo obomod. This ouggooted thot wo- mtod, mloouhr broaamoo on present . To determine the mutant of mutant-ammonia hodtoonprodoooddm-lngthooouroootmo mtimtho'mtrotom tromforrod lotbo dork into odlotilnng M.mthomtwflukmfitropmorinoodvlthwbontow chloride amok no added to tho original filtrato. This solution on Winthodorkundorvmbymotoumupirotorw on oil both at 140% . Tho distillate no oollootod in o roooivor, coolod in 1 dry loo and loopropyl alcohol both. Distillation m 108 continued \mtil all of the carbon totroci‘florido and most of tho oxeooo toluene had been collected. filo rod colored distillate no trmn Starred in tho dark 'to o quarter liter volmmtrio mm. Caro m to bo exercised in transferring this solution to tho oohmtrlo flask u oororol than a rmtlon occurred with o almxltanoouo loss or color - and mlutlon or hydrogen bromide. Tho oolution on diluted to tho volmmrko: thovoluootrio mom than aliquotamtokonom named Moon-loony occurring to tho abovo doomed Mitt-Loci. one volume multiplied by tho gamut: of tho standard 0.12: sodium tldomlroto solution used govo the mom: of Mllioqulvalonto of froo brommo. the War a: the detox-mum mu out for nation. at LO°O. for total halogon, ootivo hologon and W amide m done using the ow upormmtol proceduro 029W for tho cox-roo- pending dotammlono for the memo» a 80° . homotthovmaarlyommadiphowlothormmu fluohamlnotoodofboxmglooholinthodiotillotiooofthom- brofloatod W. Tho m of diphom'l other no: dlaoontlmod bmomotthomopontod momma! mthodiotillatoand than no tho fur-tho! poooibllity that ow dibronmatod tomoooa, 3.! tom, wold also to oarrlod on:- m tho olotimtlon. 4 Tho analytical oothodo and for total halogen, active hnlogon, “Wowmommdmtmkmmmotodm tho ”liability of tho mtiwdo. A mixturo oootnnlng 1.132 3.. 109 6.98 2:13.11va , or trichlaroaccbwde; 1.81 g., 10.61 131111- aqvuvnlwta, of bemyl bmrdde; 2.016 3., 11.93 miliequimlanta, or We Momentum} 1.520 3., 8.89 miniequralma, 0! MW ultimo) andzozfl... otbmylalooholmanalyxodinthommar WWO. mammmodtortotalhalogm, anti“ halogen and wide. no residual ablation m- u» Wm manned {crummmd same. thaanalyticalmsultam unmixed in Table 1. rmx‘ SUE3§ARI OF QJAETITATIVE BET JiMINATIDX OF EOHIEE IN I. “117633 CWSISTDIG 0F BEWZE mama, e um Wilma”, TRICILCFLOACETAEWE AND 836m ALCOEG. Www‘ 4w WW? tree on Fomd 1:: Fauna bin in Hahgm Bromide J‘aken Distillate Figurine Duo to Amide Found W m. 1:006]. 10.5? m 0.00 10059 Bmyl armada and I Winona 31 .MS 31 obs 0 .00 0 .00 31 .16 wv .._... v—w—w—“w w— in). data axpmaad in mmmnlmu. ‘ b'ma ream“ m analyzed time the reaction between tho Bin-mama” and toluene any! gave m poly’orommd toluene: mich would he found in the residue of. the distillation. By analyzing the non-dia- mu naidua for mega a good meta-m balance for total bromide m obtain-d. fig 0 «BI-mom; *"wgrmggda “I 01118113 Ear}: t with . Intoaquartcrliw,tuomkflm,mmdfl1thanama black ninth,andt1ttodu1thamrru,mnmoommerandimaod 110 1a a mutant 8025.106. bath mm placed mot]: 12.07 g... 0.05 mole, of H-brmmtriehloroacetamm and at-zactly 50 ml... 0.14? 123013, of tolutma. who beta-aghast!“ mixture flu stirred at a constant rate thmghout the course of the reaction. 1% each half hour interval one drop of ‘thoreacummixtummrmodmdtauddthamahlyprmmd aqueous starch iodide solution. The reaction was complete in two and a halt hour. as evidenced by a negative M with the starch iodide Mother. Thomakmrmadtmthaoilbath, stopperodandaat aide in the refrigerator Gunfight. Tho cold reaction asthma was filtered and tho precipitatad mm. mm me. with cold carbon manna“ according to ms W W may. 3110 an aolid had that am. melting point up mmma» 139-1ho°c., and a mixed halting point of it with an mthmtio ample of trlchlorw ”We abound no depression. the might a: the trichloroaaatma Ira 1.500 3., was man, a 92.5 per amt m at tho man. “the £11th and wash solution: we mm, distilled and unified according to tbs 139$!de outlirwd in detail pmvioualy. Tho 0.05 male or Mmmotrmhlameatamde are equal to so milli- minim“ as a hmimting agan . WW' Total halogen 345 .63 millioquivalantl (bowl brand. am bmholnenaa) Active halogen (bml brmde) 21.75 unioquivalanta Unwanted Amida (amount) 0.00 nilllequivalanta “‘1 x A: «gs. Amy-silo g Bananas. Total halogen 7 .33.; mimeqnvalants (chloromido, polyhrcmnatad toluene) Umoparatod' undo (main) 1.213 nulliaquivalmta Intmtotion of Amount t5. tea Tho 15.63 millimvolonta of total halom 1'01}:th a 91.3 por cent amnion to nowhrommtod product. tho 21.75 fillioqulvolanta of anti" habgan 1'0me a h? .7 w cont aido ehaln Emulation band on tho mate: mam. bronlnotod product. man: who 1.213 31111va or who trichlomootanldo represent 3.6:. ndllioquivdanta ..- halogen. Tho total halogen found was 7.534 ammmm which than «trotted {our tho wagon from tho .mdo loft a not or 3.90 Manual-nu or 90mm tolnaao. ‘l'ho Mined total trout» m 19.53 umequinlonta mulch no a 99.1 per cont atrial balamo. Into a quarter liter, tw nook flask, morod with Opaqua blank cloth,vtxichmflttodulthaatirraandroflnxcondmorandw in a 1.020.290. both mo planed moth 13.07 3., 0.05 male, or R-hucn tridzlomoeWo and math 50 a1... 0.1.? solo, of tolnauo. “yaw _-r a w - 7 _. v‘W-h. “"‘l " ‘ Tho heterogonom mixture In: stirred at a content rate during a manual: poriou oi“ Exactly twenty-four hours. The flask was resumed. {mm the batI-., stopporod, noppod in block pl'zotographio paper and set aside in tho refrigerator overnight. The oolntion was filtered Lo tho dark to remove the precipitate. Tho distillate and all wolvod "para we ought in a riltor flask and trap both of which were ooolod in a dry loo and isopropyl aloolwl both. The solid was dried umohaapoooiblainthianmorandthanbymotoncmpunp. Tho precipitate, in this om, m not washed with carbon totroomoricie been» of tho aolubility of any moaotod fi-bmmomido in this solvent. no solid was transferred to o 250 ml. volumetric max when it was dissolved in when tetrachloride. Tho resultant solution was analyzed for mined Mrmtrichlorooomnde. The reddish brown colored filtrato m rinsed from the filter flu}: and trap with carbon tetrachloride into a distilling flask. The damnation m carried out in tho dark oncoming to tho methoéa already doaoribod. Tho free bromine, carbon tetrachlorido and toluene mo ought in a roooim cooled in a dry ice mac} mapropyl alcohol bath. The diatillato ma trunnion-or: to a volumetric Mi, diluted to tho volnmo ml: with carbon tetrachloride» and tho amount of free bromine dotsrminod Woolly. The 11mm routine from this distillation on than distilled atria:- vacuum to separate the mono- brominatod tolueno using bomyl alcohol as a chaser. W’ Ema n-Bromotriohloroaootamdo 0 .147 mnoqmrmu Free Bro-nine 2 .99 milliaquhmlmta W' Total Mega 31:47 animal-mt. (bmayl bmxaido mid brmootolu 9213) Active Halogen (box-25:71 brmucie) 5.05 2211110qu ‘ Unlopnratod Amide (armada) 0.00 millioquivalonta 531111; or aegimgx Total fillings!) (trichloroaootmim and polo'bromimwd toluene) 9 .9 5 nulliequivalonto Umporotod Amide (azmmnia) 1.534 nfiJliequivalontl @ozprotatianit Analyses: The 0.05 mole of Hdbromoomdo corroapomia to 50 mmoqnivalonta u a bronmting 9.53mi. and 100 millioquivalmta as an mung agent .- flmt, the 0.147 millioquivalonta of unroaotod Rebromoamido as determinod Woolly vor- oquinlant to c .23; millioquivalmzto as u brmimting amt. The reaction as 99.5 per cent cmleto based on tho disappear- moo of tho fi-brommdo. 121“:th The 3b.!!! Miliequivnlonta of total leogon represents n 68.3 per cent conversion to modal-mud tolnm based on the 50 mm. confident. of Hmmido which we uaod . The 5.05.!Idmmvulontl of benzyl. bromide reprosont u 1&6 per cont side chain bromtion based on tho 3!; .17 millioquivalonta of nonobmimtad product . genuine: The 1.51; mimequivalents cf triczfloroccotanddo round in the We contain 15.62 millimioclonto of halogen. Tho total halogen found in the m. m 9.95 millioquivulmta, which man cox-rooted)!» tho mogul of tho amide 1m c not or 5.33 Mombasa“ of polybrmflutod tolum. The combined total broodno front 311 W m 142.33 d111- Imivnlontl mob ill to 81»? pa cont ntorm W. m. panama-omen ofmoroannngnlovutumomncom this ”action mo .11 motion: run at We. Ihich van not carried to completion could aria. from Jon of bran!“ curing tho 73.0mm distillation, antrapoent of broactolnmo or bonny]. brands in the loud think: no not mad cit}: carbon tota- ohfmrido boom” of the ”how’s-y a: the unmtod H-bm- mda, and ammunition of tho awesome: unbmmide giving free broom baton the mounted Hfircmoazaida could be analysed. Reaction 0 Eqfiromodichloroac otasfido . ..tZ-I Toluene in the Park at ..;O. O mmmwmmmcmoumthomm at 80°C.. 10.31; 2., 0.05 min, or fi-bmodiahlormotmido no mom to react with wtly SO EL, 0.147 mole, of “ham. Tho reaction on with in I13: hour! as indicated by a negative test with u numb Mid. solution.‘ homiloftbomticnmomwflcdmt mtlya described mica-13'. The 0011:! obtained weighed 5.210 g. and m a mixture of dichlcroaoctanido and a vary small mount, < 0.1 3., of I. mbathco which mxbli-ccd above 200°C. This high lfi'iltincs substance contained 13.75 per cont nitrogen and. 79.90 per cont haloaon. Its Itruotm'o val mudmtificd. The major portion of the solid. had the «mo mlting point as dichloroacotazzfido. 97-98°o., and had a mixed melting point with mthmtio dichlcroacctazaicto of 97-93%. M is of Distillate: Total mlogan (bmzylbromido and bmotolueme) {$.87 mmoquiv clout! Active Halogen (boozy). bromide) 22 .22 minicquivalonta Unacpmted Amide (armada) O .00 mmiequivolonta Mg of Ration” Tom Hologm 8.22 millioqnivalcnto (diorfiomaoota‘aiéa and pokmmomzatod toluene) Umoparatod Amide (mania) ' 1.80 millicquivalontl Image-motion of Moo: notes The hh.89 zillioqutnlonto of total halogen represented an 89.8 per amt amnion to mmbrocdmtod promt. The 2.2 .22 aim-minnow of boozy]. bromide roprcomtod a £39.? por amt side chain brocmtion booed on the mmt of W broofimtod pMct. Residue: Tho 1.80 millioquivalcnta of unseparatcd diohloroccotmaido reprooozrtod 3.60 milicquvalento or halogen. “rho total hangen do " in“ man-— Mm 832 “minim “minnow-rooted for tho mummouidowtomtochandut-n pow-atom. mwmm~mslummm~m¢u uancnt-tumm. h‘wmmmamwmm mammoummmahmcasm,“ Wmmumuumsoa" 0&7uhdhhummmm. mm... mWHWWWMlMMuw. It... mwummumundmmnmnm W. mmmuudwnocmmumw 117 action 3 “the 0.05 3010 of WW0 correspond to 50 111.11. 0:11:17an .- a. human; agent and mo Illuminat- u on waiting teat. m, tho 36.61 Manhunt. ot minted 8W undo sonata-1mm! iodimtrtcnny m confidant to 18.31 1111101331- volunt- u comm; mm. m. Mmmsmperm Wham an tho mat a: W I-hmodiohlormctuddo. W‘ m 1‘! .11 mmnmamu of tot-.1 Mom Mod 0 Std. per cent monies: to mmw prodwt bond on the amount at murmured momma... " Tho 1.38 minimum of bmyl brocade represented a 25 .0 percent lidoohainbmminatimbuodontho matofnonoa brow product. may 81m. m mid: II round in tho raid“ the 5.03 mullet-minim 01 total halogen foam represent-d um mount of polybromutod um. mmumbmm-mmommwx um.- ominlcnto mob W a 86.1. put «at low balance. mmmummunmmmo on. W previously. Emtiog of H-Bromomcnoowmoo with Togas g tho Dork g In the «perinatal mom doomoad previously 8.621 3., 0.05 mole, of Immomaoms as moved to mt with motly 50 m]... 0.1;? mole, of tokens. rho reaction as complotod in tool" hours as indicated by s nogstivo toot with s starch iodide solution. A white solid as filtorod from the cooled reaction mixture. mu solid «132m 1.52. 3., mole solo, and had the not melting point a ohlorosostmnids, 119-120‘0. A and melting point of this and no. onthsntio nonoohlorosostmids m 119420°c. will of to! Tots}. 3310393! 39 .39 minimivslmts (bmxyl bromide ma monotonous) ' Active Halogm (owl bromao) 35 .89 nillimivslsntl Uncoporstsd ma. (smonis) o .oo nillioquivslsats Mg of Residuo: . Total Halogen 10.16 “1110mm (ohlmsootmido and polybz-omimtod tolum) Buoporstsd amide (mm) 0.00 MM , , o , Minute: 1110 39.39 milieqoivslonts of total hdogm roproscmtcd s 78.8 per cent conversion to monobromtod produt. rho 35.89 311.111va of boozy). brmido represented 11 91.1 pot cant side chain bronimtioo based on the amount of mono- bnoninsts W. moo Since no aids as found in tho rooiduo the 10.16 mllioquivslonts of halogen represented the amount or polybrooinatod toluene. The combined total bromine from all. analyses no 18.55 1:11.111- oquivalan’oa which represented a 99.1 per emit mterial balance. Rating ofiargmmmghlmmmmda with Toluene a g: Dark g} In motly the lane mans:- u pm]: described for the re- action of an fl-brommido uith toluam 8.621 3., 0.05 mole, of R-brom~ mohlomoatmdo w W to mat with many 50 an... 0.1.7 31010, at blame for exactly tmty-vtonr harm . The reaction m not oom- pleta and the reaction fixture had a dark rod color. The chilled Mondrian” mterodulnpranmmunrudydmfibod In! the .0110 dissolved in carbon We. Th. memo III distilled under W. My Unwanted fi-Bmmnochlmoetmfide 8‘4 .06 mmmvmu Free Bromine 0.79 1:11:4qu m ‘ a of Distillate: Total Halogm 5 .27 £13.11va (m1 bmndda and bromtohm) Latin Eulogm (W1 bromide) 2 .51; 31111010171181“ Unwanted mid. (mm) 0.00 mm W: Total Halogen 1.71 mmvaenu (mahlaroaeetcddo m0 9mm fiolum) Unspent-d Add: (malt) 0.00 mmth .FAC" “‘1 ——-«- 120 The 0.05 mole of Hérmwmchlormetamiao corresponded to 50 mllioqzivalmtl :- a brandmting ugent and 100 miliequivalmta as an oxidizing agent. Time, the 815.06 mlliaquivalents of unwanted; B-brozaoamide u determined iodimetrically were oquivalent to 3.2.03 milliequivnlmtl u 1 brominating agent..- Tho reaction was 15.9 per- cent comlate based on the amount of unracoverad Wehloro-n ‘wotamicie. Bistillata: . The 5.07 millisquivalenta of total halogen represented a. 69.6 per cent. cowaraion to mnobromnated product based on the amount of wmwod Mmmmide. The 2.51; mmmnmu of banzyl broads represented n 1.8.3 per cent Dim? chain bromination band on the mount of mm- bromimtod product. Residue: Since no amide m found in this rm Nu 1.71 Magnum“ of total hum found Wed tho mount of polybromud 00100116.” mmmmmmmmommamw.somm- minim“ or a mtg-1:1 bahnca or 98.6 per cent. 1.125911% or m with Toluene 2 1,52 m k g 80°:o.;°§, In the mar dancribod previously 1.25 31., 0.02mi mole, of bromine as allowed to um um may 50 ml... 0.1.7 mole, of toluene. 121 The reaction was complotod in four and a. half hours as indicated by a nagative test. with a atarch iodide solution. The reaction mixture on than distilled at utmaphorio pronoun to romovo all or the Mmgm bromide and mat of the toluene. Bonzyl alcohol was added Ind the reaction mixture distilled undar vacuum as previously described. Wis ofmgiogllage: Total Halogen ‘ 23.25 millioquivalonta (benzyl brmido and bromtoluono) Active Halogen (bomylbroafido) 21.81 mumivalmto am a of Florida" Total HalOgon 0 .61 mnioqxuvalonu (whfororlnatod toluono) rotation of am the 1.25 ml... 0.020. mole, of bromine corresponded to 231.38 zillimivalonta a: o broodnating egg-ant . mmgtustg: m. 23.25 milliequivalanu or total halogen Wed 9. 95.6 per cont comm to mambmminntod product based on tho attmmt. 01' bmnina consumed in the reaction. Tho 21.81 millioquivalonta of bonzyl bromdo represented a 93 .7 par cont. side chain bromnation based on the amount of mono-v brominated product. my There was 0.61 11111114411qu or polybrmninatod toluene in the residue. 122 The combined tom bromim Iron .11 the only»: Isl 23.86 mnemxivflmto which was a Maria]. balance of 98.2 per cent. 0 O In exactly the some manor at Wed previously 1.25 331.. c.0232; man, at bromim in: mom to react with cut}; so at... 0.1;? mole, of toluene. The ruotionm oozmletedintuandomfl: hour! as indicated by a negative test with I. starch iodido ”Elation. The reaction mixture In than distilled It Moria pron-ore to we all of the hydrogen bromide and mat of the tohono. Em}. aloohol m than wood and the reaction mixture distilled under "am I! previously deteribed. . : e of ; t . to: Total wagon 23 .26 WWW (bmy’l. bromide and bmmotolme) Active wagon (bonny-1 bromide) 20.69 minimum graph of Routine: Total Halogen (polybromimted toluene) O .72 mniaquivalenta Ingegpretajgioiog M‘ The 1.25 :1... 0.022;}; ml... or bronmo corresponded to awe n11.11— oqunlam a a 5mm agent. W‘ . The 23.26 unioquivdmto of total halogen 1'0me a 95.6 per cent convex-11oz: to nonobrmtod promot Mood on the mount of bromine oommd 1n the reaction. The 20.69 milliequivalente of benzyl bromide roproeentod on 89.0 per cent side chain brownnotion based on the mount of mono- bromnatod . product. Residue: There In: 0.72 zonieqnivnlent of polybrominated toluene in the residue. The combined total bromine from .11 ofamlyooo was 23.98 mm- equivalents which corresponds to a material balance or 98.3 poo cent. The Wtion upon-5m: carried out are ommieod, at 30°C., - in Table VI, and, at ho°o., in Table VII. oition the Hammomioee _ To. plmtochemm decomposition of the Hubromomic‘ioe was investio gated nth the objective or being able to determine the relative rates no formtion of tree mm, proamnably by n free radical typo of reaction, involving mob combos. It was anticipated that such infomtion would be of uid in the elucidation of .5. mm mm» in or the Bah]. Ziegler reaction. on of Hafimmaridoa 2hr” experimental methods were utilized in those studios. Deonmpoaitim, (a) by means or an ample tangent! imp with a taming 1m and no filter, (b) by means of a. unwary lamp using n 350-550 Wmfilmmdntomxeinglm. and (alarmefimeiut m aloha-ate mmmch the light acumen: comm-11mm coolodbymotmairrm. Amtommuedtoimo ttntaoomtmtvolugombdng muoduthomonrylw. mumupmumaummmflmnamnm interfmo filter, omtangularholo out mmwemtal wield Mflmlythroughnmndglnameonoommgtmmlo bdngirndiatod. Infllofflaeobovamthoda mowmmmtodonm ammo bomb at properly opened intervals loch that the marina obtainable mt intuiwinluailnblototho owls. Into. third mthod, (o) mfiditioml lacuna. thou: of: nimrwmtodadjaomttofixofmoinglmmmohamwuto Wumotthomaynghttmthommlmmonuo photonfltipliet tube. A record or the Win tom gen-rota! ukeptonnmtimmlmoodw. Moaumusodpfimrilyto checkutothooonflmtintuflityottholighttmingmtmwh mmmmuwum. mmummutwmimatmmmu mmummtmnmupmormamumm amufiowmommwmotaomnm. apoo'h'ophotonnter. imagmahopmoeuuodinthomgoaaomghBBMm. Wondntungltmlminthofiowsmmllimicmmge. Afixod olituidthmuodforaohmelcngth. the W com-pm pm m- a sciatica of bromine in carbon mmofidomreportod (7?)toboct'h15unllnicrons. Thus, by irradiating a. mutton of m Mmoiézo in carbon tetrachloride: of know-1 concentration for definite lengths of time and following the fomtion of fro-o bromine 11': moms of tho Badman 5.1}. specuopi'wm- motor tho rolativo rota-as of decomosition oi“ the bromazaidoa could be detm‘svinod . The results of tho photochmicol dooompoaitiono are mwizod in Figures XVI thrmigh m. Flame XVIII shows the Bears Law curves, optical density versus concentration, for a Iolution of bromine in carbon tetrachloride at various wave lengths in the spectrum. Figaro X1?! is a plot of the Optical doaoity versus wove laugh for an Hdzmmotricfilorooc ate-11:15 solution, 9.19 x 10.33, in carbon tetrachloride as a result of irradiation by method (1)). The lengths of til-so of irradiation for each curve are 317m in Table XI. Figure m is a. plot of tho optical dmoity Versus, time for the 11.15 ulnirfioron bromim band arising from tho decomposition of the fiabmmotriczioroooetamido solution, 9.19 x lodn, in carbon tetra- chloride according to method 00). Fig-re. XVII mom A in a plot of the optical domity Verona time for the L15 Micron brown band arising has the Weitim or on EmromotricMDrooootamoo solution, .32 x 10.3%. in carbon tetra!- ohloriclo aooordim to method (c). Time XVII curve B is o plot of the optical calamity rm time for the 2.13 Moron bond arising from the dooompooition, by _ mothod (c), of a. when totroohlorido solution, 8.39 x 10.31%, in 126 lwmwlmummo am b.66 x 10"}! in broom, which repre- motomonJZXIO'ngmaomiomghuotbrm». It In! observed dorm the noun. or photochomoal decomposition that tho spectrum of solutions of the H-bromoidos which were only alight]: docomoood u a result of Motion shoved littlo or no Wmumoumootdmmpouummmntumomthe dark overnight. War, thou collation: thick: were owed mffloimtly so that n brown. obaooption band I” want thawed . further significant ammonium when, at laid. in the dark wornight. The phoooohomm decomposition n- dlonontlmod ohm: it was realised tint the light woes and mo not throng mg: to induce! ammunition at 3 reasonable mu. Tho tungsten lamp we no limitl- oantdooomponuoninmam. WMBochmnoonomousod to hold the maple- uhioh me being modified. Homer, it no mooringhngthyltmduum thatloimorbrominodmto vapor-Anon had occurred. Mama, to the damnation or mom.- mehlmmmoo, 9.19 : 10'314, m in Figaro m, the thmtioal mat of bromine which could have how liberated, 14.60 x lO'aM, was not "mood. The maxim concentration of brom‘lno attainod was 3.66 x 10.324 and, on mom- irradiation thll ulna decreased to 3.1;8 x loan. This decrease could on]: has occurred 1.32er on «motion loan. Homor, than in 3 strong possibility that with cum- bromtm’cing agents which have an active hydrogen that self brooim’cion can occur. This sol: bromuon would be aided by tho 3103‘ rate of decomposition and by that light. source used for the dmozposition. This mum also lead to a decrease in the amount of fro. bromine am: a 10" through formation or hydrogen bromicie. However, aevaral significant observations could be made. A study of Pig; “'3 XIX micatoa that the first appawance of a bromine peak was at 3:30 millimicrom rather tlmn at the 1315 mnmcrona as reported (77). A: the decomposition procm the peak gradually awaits to 3.01er wave langtha until it m at £300 Wade-roam, at man point no anti-nar- decomposition was abamod. In the deconge- Iition of a mixture: of brmuine and N-bromtrichlnrometmida, Figure XVII curve B, the origiml peak was at 1:15 uniniorona. However, an the decompouition proceeded the peak mod to Ihortar wave lengtdu «mi reached a law of £05 Wm. H Figure XVII also about that the prams of bromine catalyzes the dwomosition of the R-brcmomids. The ahapa of the curve in Figure XV I saga—vast: bromine catalysis and the farther observation that ciao-orqxosition continues in tho preama of bromine! when irradiation has 665.896; again suggests bromine catalysis in Such dompositim . 128 A A15 millimicrons B 1.20 millimicrons C 1.05 millimicronl D 395 millimicrona E 380 millinicrons P 360 minimicronu 149 ' _A :B C CIR E O D g; 8 O. :3 a 03.2 S: O I. CERT 0.2 ‘ 0.0 r I r 10 25 AD BROMINE CONCENTRATION (moles x.lO ~4) FIGURE XVIII. OPTICAL OENSITI VERSUS CONCENTRATION OF BROHINE AT DIFFERENT WAVE LENGTHS 129 ' [-3 OPTICAL DENSITY I? . 0.0 3'60 A'oo 1.1.0 450 WAVE LENGTH (millimicrons) FIGURE XIX. OPTICAL DENSITY VERSUS WAVE LENGTH FOR THE DECOMPOSITION OF N—BROMUPRICHIDROACETAHIDE DURING VARYING PERIOIB OF IRRADIATION 350 130 Tm XI LENGTH OF TIRE m? IBEADIATIGH FOR THE DECG-‘POSITIOH OF THE BROMOMCIEOROAC NAMES fivfi I awn," __._.n,__,_w .._ 4... 4...: III... I . . . __ . .._. .... . '—*... .._I LL... 7' ....._ W__‘§ W V W w .._ I". 1 It .._ .._. W Curve New mummm -‘_-_‘. O 76 209 M38 1370 618 810 1062 1602 2109 2617 3MB ’47 IO 5331; ’ Fugugwmdmmrunw P 1 l 1 i 1 1 1 i l m Dem) nation of. 8.3de mOm dlcoznposition or the fi-brom mono, di, and triohloro-o wetsuit!“ m Inn-tuned at 80°C. tor varying time Int-mm. Fifty ml. at u ”rattan; cf known mmmtrution of the H-brommdo in mi: mum-mo, an placed in a. 100 311. single nook round mm aux. The flask In fitted with («Monm- and mum in m 80°:9.1°O. on. huh. Arm five mm o: max-non to may nffiumttmrartheurinthomtmtobodrimmtthocon- dunner m tightly Itopporod. At the pad of t definite langth of tin. «unnummwaa‘tmwa oflbnthmphcod manic. bath for 1‘1" mm. All of tho MO “perinatal. operations were 131 carried out in tho dork. Tho spectrum at tho oohtion In tho unarmed from 300 to SAD Water! in tho manor doocribod provimly. Tho mmlto 0: than experimo voro mt reprocmcoblo. At om tino o given oomph would dooowooo rapidly: what-m, o short time later tho dooompooition at tho oomo oolutim proceeded quito clearly. Undoubtedly um Inn by motion hod W, but in «Edition tothnmgonindmrtmcotulyaioployodmmortontrtlo. The differmo 1n rotoo of ammuon of tho mo owlo no not mod by Immun- in m- oomph mm tho aim-mm. had boon ram-um. modondondasodimodiotolypaortom. Amorofinoduotbod of «convening tho onidooin tho oboonco of mm and amino cotolyoio to W to obtom o qnmtitotivo me- or on. rohtivo rotoo of mutton at tho Imam However, meal Motim «and to undo from tho thornol ammonium of tho Iabmoomidoo. no peak for o oolutiotn of brominoinoorbontotnchloridomrwtod (77) “bonus-am- new». m, In tho thonnl ammunition at tho I-bm m, (11, out trichloroocotouidoo tho firot We of 1: hrouino pool: no ot 380 Moreno. Tho poution or thi- peok gradual): mud tolmgaruvolongthommgtho doooupooitionmdroochodonxflm arbotwthSondthdmnim-m. Mmommtotho oboorvottan ado in tho photochanieoa. dooonpoution. Tho thorn-1 ammonium at o. oolntion of l-brmodichlarouotouldo and broad.” in urban totroohlorido mound on initial pooh, boron (lawman. It L515 Wm. During tho dooaupooition thin peak gradually 132 wmwmuu ”abdominimothS Mum. Mo, again, In oinilortotho ohmotioamdo duringthophotoc chain]. «composition at o aviation or l-broaatriohlmootonido ond bronino in cotton tetrachloride. Solution- ot tho thrao i-bronoonidoo in «than totmhlorido moproporodondootuidoinnlooodnflonuthomm light. Tho first to develop o brain color no tho l-bmmo chloroooctomido, and tho lost to develop ouch o Color no Kohl-m- trichlorooootomm. solution: of tho throo E-bmmnidoo in Mm mo oot ooido in Cloud vouch for o poriod or too maths. In I rohtivoly short timo o bromino mint oppoorod in tho oolutipn, but after o mguporiodottinoitdiuppoorodmdoounmzmtotowito Wandmpromtonthobotmdthoflom. rho only”. of then condo vex-o oo follow: ‘ For Cm Pour Cont §olgtion in C‘nlorofom of Ritz-om m H—Bromoaonoohlomoootomido 15.21; 77.7h I-Bmmdiahloroocotomido 15.13 71.05 l-Bromotrichhmuotofido 1h.01 77.67 m at tho oolido mum obovo 206°C. and did not melt. Their otruoturoo mo W and tho colmzlotod nitrogen and chlorine voluoo for tho oorrooponding no commando anion night hon orioon oo o rmlt of tho decomposition of tho N-bromamido oro lower than tho obavo voluoo. 133 A omito cryotollino oolid containing 18.05 per cent nitrOgen I“ obtained from tho thermal doomoition Of o oolntion of H-bromou mohlnmmtmido in carbon tetrachloride. Tho amount or oolid, 1.21:0 man, no imufl‘icimt to pomit o hollow minis. Tho molar extinction coefficimt for tho outowl bond of tho throo R-brommdeo in carbon totroohlorido m dotominod and are recorded in Tablo XII. TAHIE XII Mm EXTINCTION COEFFICm FOR THE 6mm BAND C-F SUE-E} N-BI'IC‘W‘IIDZ’S IN canon WACEEQIIDE EtfiMI, fizz—i‘lfii: tAWew,$E_:: .._“:“4‘5‘ “A_i Compound Holm- Extinction Cootflciont lyBronomnochlorooootuddo 372 WM“ 100 WOWMo 1:55 SUI-5&3! 13h SMIARY N-bmmocinimm ond 11,)“ cdibromdimthyhxydontoin voro roootod with cyclohorxeno in carbon “Wide and chloroform. In urban Wochlorido tho chrommooWo you tho highor yiold, 63 pot cont term 55 per cent, of ollylio brominotion product, 3W cyclchomm. In chloroform only bromino addition «mod. Ritmgon onlfido totrobmo, may“ om phoophonitrilio bronido, Pillar” m proporod Ind rusted with cyclohoxouo. The tumor mo oono ollylio trauma”, but bromino addition no tho min rotation. Tho latter go" no organic bruit» products. Tho H-bromo mono, di, ond trichloroocotonfidoo mo proporod by addingbmto theiroilvoo- ooltointritlmotioonidooo metion oolvont. Attmpto to preporo H-bromoootmido, H-bromothm- motmido and I-bromhylooflofldo by tho oomo method mo mocoooful. Tho 34:11:30 mono, di and trichlorooootomidoo mo allowed to react um tolnono ot too mm. We. and 60°C. In. E-brm chlorooootuddo can tho highest ratio of oido ohoin to ring broad.- nouon, and tho l-bromtriohlmoootosudo mo tho lowot rotio. m photochemical um thou-o1 dooomoitiono of tho H-hronoonidoo mo invootigotod. It no [and that bronino catalyzed the «convention and thot tho brad!» famed Ming tho decomposition woo couploxod. A melanin including tho bottom“ and We diooooiotion ottho nitromhomnobmduopmpoood, booodonooorrohuon bot-Con tho infurod, «composition md hrominotion doto. LImAmm arm: 135 LITFRAL 3»? CIT?!) 1. N3. Ph. Bun-H01, mm. 52g. 1 (191.14). 2. w. Stoinkopt Ind A. Otto, Am», 939, 61 (1921). 3. x. (impugn ond w. a. Low, .1. in. Chm. Soc... 19, 1555 (19218). n. a. 14. 8am, J. Chen. mm" a, 2008 (1953). s. o. a. m: and u. Liddol, J. m. Chan. Soc... 51. 11.61. (1935). 6o 0o 3. W11, U. mu M So no 8W3. Jo no Chm. 500., 533.. 2281 (1936). 7o R. E. 538311.”, Jo AMo Chaino SOGo, 11, 1377 (1955)o Bo Bo ‘o Rm, 3o )1. Jonea. Do So Km find Ko Dowmr' Jo Mo Chou. BWo, my 60 (1952). 9o 3o ‘o m3... Jo Chm. PWo. 25’ 861 (1950). 10o 3o ‘o M13; Jo ChMo PMo. a, 91.32 (1951)o 11. A. M. Buohwoll V. H. Rodotmoh and M. R. Roy, J. Am. Chem. Soc” go, 211.1: (19385. 12. a. Lonomnt, Campt. am., 23;, 515 (1915). 13. H. Loam, oompt. Rand" 3,33, 136 (1916). 111. a. Loam-mt, Compt. Rand" ggg, 1219 (min). 15. 3. 1m, eompt. amen, g_2_8, 1861 (1919). 16. n. E. Riohordo and a. w. Thompson, J. Chm. Soc... 1231, 121.8. 17. I. Sonti on! D. Barker, J. m. Chan. £00., £2”. 2008 (19110). 18. J. R. Looker, G. W. Towpkin and J. D. Park, J. Am. Chem. Soc., 19,. 5573 (1952). 190 no Go Sm.“ m Eo Co Miller, Jo opt. SOCo 33o, lb 130 (19331;)o 135 20. G. B. B. M. Samoa-loud and H. A. 'v-flllio, Tram. For. 300., g, 181 (191.5). 21. '1‘. D. hug!“ 'NoBromouooinimido, Ito Roootiono ond Boa," Arapahoo Chamioolo, boorporatad, Bwldor, Colorado, 1951) p. 331. 22o C. H. K30 and 8m mm H." Jo mimo $00., 1221. mBo 23. A. H. Blow: “Organic Synthesis," John may and Sons, New York, 19213} Colloctivo Vol. I, p. 3. 224w Ho 01m 311d Ho 0o Jonas, Jo no Chwo SOOo' &. 11458 (1924.3)o 25. r. n. Scum and n. F. 301111;, J. Chem. rm... 2}, 1516 (1953). 26. A. H. Butts ”Organic Synthesis," John Wiley and Sono, New York, 191.33 Collectivo Vol. II, p. 260. 27. I. Hoilbrom “Motions” of Organic Compomxis," Oxford University Prooo, How lurk, 19533 Volnmo II, p. 1.811. 26. A. 3. mm: “Organic 3mm“; John Wiley and So», How rm, 191431 Colloctivo Volmo I, p. 153. 29o Do Ao W. Jo Mo Chem. 506., IE, 72 (19:2)o 30. o. mam-d, Pm. Ind. load" _8_, 365 (1938). 31o H. Lo man, No “.011, Jo Ho 10m and To 1!. Many, Jo Chou. P113!" 2;, 333 (1953). 32. H. Son-om and i. Liboru, Rivorco Sci... £13, 1687 (19531). 33. B. 1'. W11, 3. E. Richardo ond H. W. momma, J. Chm. 3%., 3h. Eo Do 6011an 3. 3o 1' 828, .859 (to 801V“ PrOOGB. 600). CAo, 23:... 632 (19325. 350 no Go Wm, 3. Jo Cam .1“ Ho Ho Thompson, Jo ChMo PWo‘ 39., 520 (1952). - 36. ll. 3. Boylioo, A. R. H. Cole and L. H. Little, Austr. J. Chem, .8... 26 (1955). 37. 0o R. km ”1d U. Liddel, Jo mo Chamo 5°C., EL 1:451} (1935). 38. M. nodal ond H. E. Hanan, Trono. For. 5013., M, 1170 (1951). 137 39. c. 1:. {Mag-gins mm c. c. Pimantal, J. Chem. mm... 33, 896 (1955). 340. B3. A. 210nm lug-hos and A. Shaman, J. Chem. 500., $22.6... 101. 1.1. 1. 1301.1, Born, :3, 51 (1919). 2.2. A. 1301.1 and 1:. Jascifinmtski, Ban, 2:1: {.75 (19:31). 1.3. a. xzamt, Ban, 1;, 122.2 (191.1). 1111. FL. B. Woodward, J. Am. Chem. Sam, g, 1625 (191.0). 1.5. K. 2:1on . Spaoth, E. Schoaf, W. 5011mm and E. Wimcolmnn, Am. 55}, 30 (19:12). 1.6. a. 3.1mm) ond P. fiarrer, Elelv. cam. mu, g2, 573 (191.6). 1.7. R. 1. Raphool, J. Chm. 800., .1232, 51.1.. 1.8. 1. 3mm: and 2. Reichotoin, Helv. cum. Auto, :2, 1616 (191.7). 1.9. 1. a. Buohmn out! n. a. Bovton, J. Am. Chem. Soc... 19, 3510 (191.3). 50. J. 3113111311 and J. 13. Gregory, J. Am. Chm. Soc», 3, 1115 (1919). 51. 6. Milan and 1. Hottatain, Holv. cm. iota, 32, 1256 (191.1). 52. 0. 1mm and 1. 9.1mm, Helv. cm». Auto, 39, 1263 (191.7). 53. P. Violond and K. Plioochor, Holv. China. 1.1., fl, 1876 (1934?). 5:1. H. Sc‘rmddt and 2". Elmer, Holv. China. Auto, 32‘, 111.2. (19:6). 55. L. F. Fiosor uni s. Rajogapflon, J. Lu. Chem. 50.3., 13,, 3938 (191.9). 56. L. F. Heoer and s. ijogopflan, J. Am. Chem. Soon 1:. 5530 (1950). 57. w. J. Bailey and J. 3.11:», J. Org. Chem, 39, 669 (1955). 58. o. R. Roy, Ham-o, 1:6,. 36 (19115). 59. D. 1!. Hey Am. Roperto Pragmo Chem. (Chm. 500. London), 2%, 131 (191.1). 60. Go Fo Bloomfield. Jo Chem. SOOo,‘ 321%, 1111. 61o Jo B. Row. m Eo Ho meun' Jo mo Chamo SOCo, 12.) 1630 (19139)o 62. I". H. Buchman and D. R. Kenton, J. Am. Chem. Soc., 19, 23517 (191.8). 63. I. Longfold and J. Stioglita, Arm. Ghana. «3., 2.5, 215 (1893). 62.. H. Box-mm, Compt. Rond., 15;, 92.9 (1911). 65.- o. Frommini, Gus. Chin. 11.1., 2;, 228 (1903). 66. A. 1. Boom on! w. P. Zimor, J. in. on... 50m, 13, 1103 (1.951). 67o Jo Do Pm, Ho Jo ”3071323, "o Fo I'm Ind Jo- Ro Luff”, J. Am. Chem. 300., 71, 2189 (1992). 68.1.. F.)iudrioth, R. Steiman om! i. D. 1". Toy, Chem. Ron, 2, 109 19113 .. 69. H. Bode, Zeitoohrift for inorganiocho Ohmic, 2'52, 13.3 (19343). 70. H. B. V” V‘lkfinbul‘gh and Jo C- W, J15, J. Am. Ch”. 8°C., 2.1,. 213). (1925). 71. S. A. Vomooonogii, J. Russian Phyo. Chem. 50s., 32, 221 (1927)] c. 1., 33, 11.13 (1.928). 72. H. V. Sidgeuicks 'Tho Chanda]. 121th and Their Commando,“ Mord Univoroity Press, Amen. Houoo, London, 1950; Volume II, p. O92. - 730 ‘o Balm.’ Bull-o SOOo Chwo. 2’ 6342.5 (19142)o 711. A. H. Butt: "Organic Synthesis," .1023: Wiley and Sons, New York, 191.33 Colloctivo Volmo II, p. 171. 75. I. Hoilbrom 'Dictionory of Orgonio Componmio,’ Oxford Univoroity Prooo, Her Iork, 1953) Volnm II, p. 311.. 76. a. a. Umbaem', Ind. and Eng. Chem... Anal. 211., 1;, 383 (191.3). 77. c. L. 02.11:: and o. J. Mar, Tram. For. 50m, 33, 1506 (1938). 78. r. 1. Blood) one) D. Velma, J. in. Chou. 800., (59., 121.3 (1938). 79. w. 9. Math, 2. Prom: cm... 221. 30'! (193?). 80o Ho co Urey Lo 3. m and to 0o MOO. Jo A31. ChMo 50¢o, 5-1., 1371 (19293. 02-551.:— 139 81. M. J. S. Dewar, J. Chem. Soc., 1?;5, hCB. 82. F. Fairbrothor, Nature, 160, 87 (l9h7)o 83. H. A. Bonsai and J. E. Hildebrand, J. Am. Chem. Soc., 20, 2532 (191.8). 8h. H. A.)Benesi and J. H. Hildebrand, J. Am. Chan. $00., I}, 2703 (19-59 . 19921- W (W1) 30 W M31111 Mmmmmmz “mo 80]!” .. .‘fi:£1.. ~9.92°:10 lymounoMot R ”3.3” \ioo nunnnnununoonmmmmmmmmmmwmmmwmmmmm3 inwunnuu anon uuuauu u:nno mmmmmmmmmmmmmwmmmmmmnnnnunnmmumum unuuuuuuumuauwnwufifiuNWNQQfiflbfiflflflmuuwfiuflfififlfiuwu nnnnnnmnmmnwmmmwwmmmwmmwwwmmmwmammnuwmmwunnnun wwwnvvmwwmwwwmwmwwwwmwwmflmwwmwwwn”MNNWNN38UWflfl mmmwmmwmmmm.m.. .mmmwmwwwwwwmmw....mmmmmwwmmmm. wammm&%wmmmmmmmmmmmwamm mm WED mm M M PICPIOMRIDE swcm1,~1.513x1o"§,nuommox ' Bro Lugth Solvont South: lot W1) 11 v n 1):..;.1,,/1.10a 11 1.5141403 nigh-10' 5.750 1739 68 22 86 1.6 21. 5.760 17 88 a: 86 1.6 2). .770 1133 88 22 86 1.6 a). 5.180 1730 88 22 86 1.6 a). 5.332 172? 89 11 85.5 52 1.1 . 1711. 89.5 6 85.5 52 66 5.810 1721 89.5 6 85 57 51 5.830 1718 09 11 8!. 69 57 5.830 1715 39 ll 83 80 69 5.81.0 1711 90 00 a: 93 93 5.850 1709 90 00 30 111 117 5.560 1706 90 oo 76 168 168 5.670 170). 90 00 11 237 237 5.680 1101 09.5 6 66 310 302. 5.890 1698 89.5 6 56 I. h 168 5.900 1695 90 00 51 33 5:; 5.910 1692 90 00 13 7 1 5.920 1689 90 no 38 86: 062 5.930 1666 B9 11 31 889 878 5.910 166). 69 11 3? 889 010 5-950 1681 39.5 6 31 889 683 5.960 1678 69.5 6 h! 265: 6% s. 0 1675 90 00 1.7 5.9 16“}: 69 11 53 529 518 5.990 09 11 59 m 1.11 6.000 1667 89.5 6 67 .5 288 :61 6.010 166:. 89.5 6 69.5 259 253 6.020 1661 90 00 15 10: 182 6.030 1658 09.5 6 77 156 150 6.01.0 1656 81.5 18 a 156 no 6.050 1663 33.5 as . 156 123 6.060 1650 :2 60 117 95 6 161.7 68 a: a no 100 6 161.5 89 11 1‘ 91: 6.090 16).: 89 11 an 93 a: 6.100 1639 as 22 a 105 83 6.110 1637 87.5 28 3.5 111 83 6.120 1631. 87 13 .5 99 66 6.130 1631 01.5 10 68 93 65 6.110 1629 81.5 as 60.5 m 83 6.150 1626 I1 33 ms 111- 18 6.160 1683 86.5 10 00 11? 77 mu WED WHO“ mnmmmmsmcmoam 601m1.018:10Jn,m-1m905001mmm in L alum. 501111.106: 102 a 106 IJIID' I! 10: 10/1 '10“ “In: 1.6/1 5.700 17521 89 11 88 a 11 5 .710 1751 89 11 07 33 a: 5.720 171.8 09 11 87 :3 2: 5.730 1715 69 11 87 13 22 5.71.0 1712 89 11 87 33 22 5.750 1739 09 11 66 1.6 15 5.760 1736 90 00 86 116 M 5.770 1733 99 11 BS 57 06 5.760 1730 90 00 65 51 57 5.790 1727 90 00 81 69 69 5.000 1721. 90 00 81 69 5.610 1721 90 00 02 93 93 5 .020 1718 90 00 60 117 117 5.830 1715 90 00 00 117 117 5.61.0 1712 90 00 79 130 130 5.850 1709 90 00 77 156 1.56 5 .660 1706 90 00 71 196 196 5-870 1701: 90 00 7° 852 352 5 .680 1701 90 00 65 325 325 5.690 1698 90 00 57 156 1:56 5.900 1695 90 00 52 51.9 51.9 5.910 1692 90 00 13 738 738 5.920 1689 90 00 Id 762 762 5.930 1686 90 00 2.2 362 162 5.9110 1681. 90 00 h? 50 650 5.950 1681 90 00 56 01h 0711* 5.960 1618 90 00 61 389 389 5. 1675 90 00 67 295 295 5. 1672 90 00 71. 196 196 5.990 1669 90 00 78 1112 1112 6.000 1667 90- 00 60 93 93 6.010 16611 90 00 83 60 ‘50 6.000 1661 90 00 821 69 69 6.030 1658 90 00 05 57 57 6.0.0 1656 09 11 an .69 50 6.050 1653 90 00 61. ‘69 69 6.060 1.650 90 00 81; 69 69 6.333 161.7 90 00 05 57 57 6. 1615 90 00 a6 .66 16 6.090 161.2 90 oo 67 33 33 6.100 1639 09 11 86 M 35 6.110 1631 09 11 86 ~ 116 35 6.120 16311 89 11. 86 £16 35 6.130 1631 09 u 86 1.6 35 6.110 88 22 66 1.6 21. 6.150 1626 87 33 86 116 > 13 6.160 1623 B7 33 85 57 11. 7mm mmmmmmmmnmmm 1.137%:10 mmzmmam fin Luau: M (w n V I! bugle/1919’ I! $10.}wa 10‘ MAJ 5.700 1751. E 00 86.5 2.0 00 wS .710 1751 .5 6 86 1.6 00 5.720 1788 11 8 57 86 5.730 171:5 89.5 6 85 _ 57 e 5'1 5 .7110 171a . 6 80 69 63 5 .75. 1739 09 05 5 8h 69 63 5 .760 1.736 11 fl ‘ 93 60 5.770 1733 O9 11 80 116; 106 5 .780 1730 10.5 6 76 162 5 .790 1777 00 71 237 126 5.810 1721 m5 6 65 385 319 5.820 1718 89 11 63 357 3116 5.830 1715 89.5 6 59 1.29 016 5.81.0 1711 00 5! 510 5119 5 .850 1709 89 11 16 6 660 S .860 1706 89 11 It! 7 751 5.870 1701. 89 11 99 837 826 5. 1701 88 w a: 30 831 820 5 .890 1698 86.5 1; 863 ‘ N15 5 .900 1695 89.5 650 61.6 5.910 1691 89. 6 511 505 5 .920 1689 6 63 397 351 5.930 1686 86.5 17 07 295 878 5.960 1688 89 .5 6 75 181 176 5.950 1681 89.5 6 7; 156 150 5. 1678 89 11 7 m 131 5. 0 1675 89 11 19 1.30 11.9 5 .9 1672 89 1.1 g 130 119 5 .990 1669 89 11 93 62 .000 1667 88.5 17 8! 93 76 6.010 1668 86.5 17 a 93 26 6.020 1661 .5 17 83 80 3 6.030 1658 88.5 17 83 80 63 6.02.0 1656 87 31 a 93 60 6.050 1653 87 33 a 93 60 6.060 1650 87 33 CI 93 60 6.070 161.1 87 .5 88 U 93 66 6.000 1685 a 33 Its 69 36 6.090 162.2 1.6 81 30 3h 97 80 93 36 6.100 1539 85 H 7‘ E 1 13 1 I 1‘ 5.700 1751. 89 11 88 a: 11 5.710 1751 69 11 87 33 23 5.720 171.8 86 22 87 33 11 1% 1715 89 11 87 33 22 5. 17112 86 11 87 33 ' 22 5.750 1739 09 11 06 16 35 5 .760 1736 09 11 as . 3.7 as .770 1133 89 11 Sh 69 58 5.760 1730 09 11 82 93 82 5. 17:7 90 00 60 117 117 5. 1726 89 11 76 11.2 131 s. 1721 90 00 78 112 112 5.620 1718 90 00 77 156 156 5.830 1715 90 oo 76 166 168 5.660 1 9o 00 75 101 182 5.650 1709 90 00 71 237 237 5.660 90 00 66 310 310 5% 1701 90 00 56 11.0 61.0 5. 1701 90 00 50 588 588 5.690 1696 90 .00 61 786 786 5.900 1695 90 00 36 916 916 5.919 1m 90 00 35 915 91.5 5.910 1689 90 00 1:1 86 786 5.930 1666 90 00 50 588 588 5.71:0 1681 90 00 .65 325 325 5.950 1681 90 00 70 252 252 5.960 1676 99 99 7h 196 196 5.970 1675 9o 90 6 :12 1M 5.960 in: 90 00 0 117 1.17 5.990 90 00 62. 69 69 6.000 1667 90 00 01. 69 69 6.010 1661. 90 00 81. 69 69 6.000 1661 90 00 60 69 69 6.030 1653 90 00 85 S7 5? 6.0360 1656 99 on 85 57 .57 6.699 1661 90 00 .85 57 57 6.060 1650 09 11 65 57 1.6 6.3;: 1617 90 00 85 57 57 6. 16115 ’0 00 86 16. .66 6.090 1612 90 00 55 1:5 {*5 6.100 1639 69 11 65 57 1.6 1.171110 1mm»... aha: unnuuuuuu ummmmmmmmmmwmmmnnamennmmnmw uuunmflaaaummmmmmmmmmmmmmmnmewannmunum 6 6.65 . 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R “M.” “hymen! S.750 1739 00 a 81.5 :0 6 5.760 1756 00.5 17 87.5 20 11 S. 1733 00 2! 81.5 28 6 5.7 1730 90 oo 09 11 n 5.190 1727 09 11 68 ‘ I! 11 5 .000 11th 09 11 87.5 a 11 5.010 1721 09 n 07.5 20 17 5.&0 1710 09 11 06 1.6 35 5.830 1 09 11 07.5 00 17 5.000 1712 09.5 6 07.5 20 33 5.050 1709 90 no 87-5 I! II 5.060 106 09.5 6 56 06 to 5.3: 1703. 09 1.1 00 g g 5. {gt 00.5 11 00 5.000 00 u no 117 95 5.900 1695 00 I! 76 160 1116 5.910 1091 09 11 71 237 i“ 5.900 1689 09 11 60 3511 330 5.930 1006 09 11 59 m m 5.900 1.603. 09 u 50 509 530 5.950 1601 09 n 01 650 639 5.900 1670 09 11 MS 693 000 5. 1675 09 n 08 (I! 610 £350 161669" g g. g 513 33 6.000 1667 07 11 60 an 309 6.000 1661: 09 n 73 00! 190 6.000 1061 09 11 18.5 116 105 6.030 1658 0’ n 01 M5 90 6.000 1666 00.5 17 0° 11? 100 6.050 1653 00 :1 0s 57 35 6.000 1090 00 a 00.5 03 01 6. 1607 07.5 00 00 69 u 6 A 1.005 3.5 10 05 57 00 6.050 m n 00.5 63 10. 6.100 1639 00 n 00.5 63 6.110 1631 00 :1 00.5 63 6.110 1030 01.5 10 00.5 03 35 6. 1631 3.5 a 00.5 68 35 6 1609 .5 00 00.5 63 03 6.230 160.6 06.5 00 00.5 63 is 150 113.8 XXIII INFRARED ABSORPTION Ml Fm PWE‘MRHDE A . Solvm 01101, - 9.381 1: 10 H, Bane Lina 90;: of Truduion A1._ Wm" ngth solvent Solution Net Carbonyl) u v 51' 16;;610/1-10’ 51' aware/1.103 16%10/1-10a 5.750 1739 88 22 87 33 11 ' 5.760 1736 88 22 87 3 11 5.770 1733 88 22 86.5 1.0 18 5.780 1730 88 22 86.5 80 18 5.790 1727 89 11 86.5 1. 29 5.800 1721. 89.5 6 86 86 1.0 5.810 1721 89.5 6 85.5 52 86 5 .820 1718 89 11 88 69 58 5 .830 1715 69 11 83.5 75 68 5.850 1709 90 00 82.5 87 87 5.860 1706 90 00 80.5 112 112 5.670 1703. 90 00 78.5 136 136 5 .880 1701 89 .5 6 75 .5 175 169 5.890 1698 89.5 6 70.5 21.5 239 5.900 1695 90 00 66 310 310 5.910 1692 90 00 60.5 397 391 5.920 1689 90 00 56.5 865 165 5.930 1686 89 11 55 1.98 1.83 5.980 1688 89 11 58.5 503 1.92 5.950 1681 89 .5 6 52 589 5143 5.960 1678 89.5 6 51.5 558 552 5 .970 1675 90 00 52 .5 539 5-39 5.980 1672 89 11 55 891. 1.83 5.990 1669 89 11 60.5 397 386 6.000 1667 89.5 6 69.5 259 253 6.010 1668 89.5 6 72 223 217 6.020 1661 90 . 00 79 130 130 6.030 1658 89.5 6 81 105 99 6.01.0 1656 87.5 28 81 105 77 _ 6.050 1653 87.5 28 81 105 77 6.060 1650 88 22 82.5 87 65 6.070 1687 88 22 82.5 87 65 6.080 1685 89 11 85 57 1.6 6.090 161.2 89 11 85 57 1.6 6.100 1639 88 20 85 57 35 6.110 1637 87.5 28 83.5 75 87 6.120 1538 87 33 86 86 13 6.130 1631 87.5 28 85.5 52 21. 6.11.0 1629 87.5 28 85 57 29 6.150 1626 87 33 88.5 80 2? 21.3.3111! mmmnm umm- -O.668:10" numbnmumm 0 7 yuan/1009 magma-"1:51.!!!” 5-659 1 90 00 09.5 6 6 5.660 1767 90 00 I9 11 5.670 1761 90 00 00 a 22 5.680 1761 90 00 00.5 17 17 5.690 1757 90 00 a a 21 5.700 1 90 00 07.5 10 a 5.710 1751 90 00 87, 3.1 )1 5.720 1788 90 00 87 1.7 11 5.730 1715 90 00 86.5 80 00 5.700 1 90 00 05.5 52 5: 5.750 1739 89.5 6 310-5 63 57 5.760 1736 90 oo 00. 87 31 5. 1733 90 00 01. 99 99 5.7 1730 90 00 00.5 m 11: 5.39.: 1727 89.5 6 10.5 136 190 5. 1721. 90 00 75 100 13 5.010 1721 09 11 71.5 3 m .020 1710 90 00 68 889 5.190 1715 90 00 62. g3 3“ 5.07.0 1711 89.5 6 60.5 359 5.050 1709 89.5 6 89.5 g 3’7 5.860 1706 89 11 67 .5 277 5.870 1700 89.5 6 60 065 2.59 5 1701 09 11 72 m 011 5.000 1608 89.5 6 . 10‘ 190 5.900 1695 00.5 6 m 156 5.910 1690 80.5 17 7 m 125 5.920 1689 01.5 90 33.5 196 100 5.930 1606 00.5 17 117 100 .910 1688 88. 17 0! 93 76 5.950 1661 u a 09 91 70 s. 1"; O; u u‘ , f u 5.9 1670 5 17 00 5| 5.990 1660 00.5 a 06.5 1.0 23 6.000 1667 3.5 65.5 63 81 6.010 168. .5 g 32.5 be 2.3 6.020 1661 3k; 16 18 m 5 1.0 86 86 6 TABLE I17 WED W107! DATA FOR H-ERWODICIWMCME 6010-10001.” -0.101x10" 16.300.113.901“ Hum Law: I» (W) .L V 078.190.1414? #1 1-0 1ago/1°11” Into/1019‘ 5.600 1766 09.5 6 89 11 6 5 .610 1763 69.5 6 09 1.1 6 5.600 1779 69.5 6 09 11 6 5.630 1776 09.5 6 09 11 6 5.600 1773 09.5 6 07.5 88 00 5.690 1770 09.5 6 07.5 06 00 5.660 1767 00 67.5 16 26 5.670 17611 90 00 3.5 66 a 5.600 1761 90 00 06 06 5.600 1757 90 00 86 06 06 5.700 175k 90 00 86.5 00 M 5.710 1 90 00 06 66 106 5.700 1768 09.5 6 60 69 61 5.730 1705 09.5 6 2.5 75 60 7-7;: 1;“ 7.6 2 . 0: .1 . 39 5.760 90 oo . 76.5 160 160 5.170. 1733 90 00 73-5 803 003 m :0: 6 0 2; '7 :7: 5.3 1700 90., 00 61.5 :31 101 5.010 1711 0055 2.6 65 3:5 119 2-2;: 67: .7 1* .0 0 5.800 1711 09.5 6 g 117 m 5. 1709 ,0. 00 ‘00 117 117 5.860 1706 90 00 g 130 150 51070 17011 90 00 105 105 5.660 1701 90 00 I! 93 93 5.690 1690 90 00 85 57 a 5.900 1695 90 00 06 06 51910 1591 90 m 86 M 06 5.900 1660 90 00 06 b6 ' 06 5.9 1686 8’ .11 66 I16 35 5.9 1600 09 1.1 87.5 00 17 5.960 3678 89 11 3.5 00 17 5.970 1675 09.5 6 00 17 7.0 6.77 2:: 2 0: :7 .7. 6.000 1667 89.5 6 00.5 17 11 153 “ELF. XXVI MARE) m3 DATA m l-EIQTOTRICIEOROACE‘I'HEDE SolthOL-B.h10:10 “77,000.110019050679000010-106 10:701-131.): ”1.7780va 7701(Carbmy1) 7 log glue9 5’: khan/1.103 log 141-103 5 .550 1800 88 22 87.5 28 6 5.560 1799 88 22 87.5 :8 6 5.570 1795 38.5 17 87.5 88 11 5.580 1792 88.5 17 37.5 :8 11 S .590 1789 89 11 88.5 17 6 S .600 1786 89 11 88 22 11 5 .610 1783 89 11 88.5 17 6 5.620 1779 89 11 88 a: 11 5.630 1776 11 88 22 11 5.680 1773 89.5 6 87.5 88 22 .650 1770 11 87.5 28 17 5.660 176? 89 .5 6 86.5 80 311 5 .670 1768 89.5 6 86 116 80 . 1761 89 .5 6 85 57 51 5.690 1757 .5 6 82 93 87 5.700 1758 90 00 78 182 182 5-710 1751 89-5 6 73 809 803 .720 17118 11 66 310 299 5.730 1785 89.5 6 59 822 016 5.700 171.2 89.5 6 57, 1.55 7.50 .7 1739 89.5 6 59 822 816 5.760 1 36 89 ' 11 65 . 385 3111 5.770 1733 11 71 237 126. 5-780 1730 89.5 6 79 130 1811 5.790 1727 00 82 93 93 5.800 1728 89.5 6 83 80 71. 5.810 1721 89.5 6 85 S7 51 5.820 1718 89 11 85 57 86 5.830 1715 89.5 ' 6 m 33 07 5 1712 00 88 22 21 5.850 1709 89 11 87.5 28 17 5.860 1706 89 11 87.5 28 17 5.870 1708 89 11 07 .5 28 17 5.880 1701 88.5 17 88 28 6 5.890 1698 88.5 17 88 22 6 5.900 1695 89.5 6 88 a 17 5.7:: :0: 2:5 2 :3. 8 7 , . 11 5.930 1686 88.5 17 88 a 6 5. 1688 89.5 6 88 a 17 5.950 1681 80.5 6 88.5 17 11 ‘ 'ft‘CL. MICHIGAN STATE UNTV‘7RS;.Y 0; AGRICULTURE AND zzo 3425.205 DEPARTMENT OF UII'EN‘IISTRY EAST LANSING, MICHIGAN JUL 5 ’57 £81}- I .1; 2 b2 . .s Date ue Demco-293 MICHIGAN STATE UNIVERSITY UF AGRICULTURE AND APPLIED SCIENCE DEPARTMENT OF CHEMISTRY EAST LANSING, MICHIGAN C IIIIIIIIIIIIIIIIIIII