The Rearrangement of 1-Bromobutane Citation Jameson, Archibald Yule (1924) The Rearrangement of 1-Bromobutane. Bachelor's thesis, California Institute of Technology. doi:10.7907/1TX9-VR87. https://resolver.caltech.edu/CaltechETD:etd-04262004-135347 Abstract No Abstract. Item Type: Thesis (Bachelor's thesis) Subject Keywords: Chemical Engineering Degree Grantor: California Institute of Technology Division: Chemistry and Chemical Engineering Major Option: Chemical Engineering Thesis Availability: Public (worldwide access) Research Advisor(s): Unknown, Unknown Thesis Committee: None, None Defense Date: 1 January 1924 Record Number: CaltechETD:etd-04262004-135347 Persistent URL: https://resolver.caltech.edu/CaltechETD:etd-04262004-135347 DOI: 10.7907/1TX9-VR87 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 1505 Collection: CaltechTHESIS Deposited By: Imported from ETD-db Deposited On: 29 Apr 2004 Last Modified: 03 Oct 2019 23:08 Thesis Files Preview PDF (Jameson_ay_1924.pdf) - Final Version See Usage Policy. 728kB Repository Staff Only: item control page

THE PEAPPANGEMENT of 1~BROMORUTANE Archibald Y. Jamegon In partial fulfillment of.the requirements — . for the degrees of Bachelor of Science in Chemical Engineering a3 Pasadena, California 1924 % = The Rearrangement of 1-Bromobutane [On tWO Oppose? . ture of organic 1. Cuy, J. Am. Chem. Soc. 42, 503 (1920) g. Stieglitz, fade ‘ id. 44, 1201 (1922); Lapworth, J. Chem. “Soc. LL, 416 (1920); and Kermack and Robinson, ibid. 121, 427 (1920) holds that carbon atoms are polar in the seme way as, but to a less degrees then, inorganic compounds, and that the carbon etoms of a chain tend to become alternately positive and negative, the stability of the chain depending on how closely this condition is fulfilled. Should we write, now, the polarity formulas, after Cuy, of 1l- and 2-bromobutans, Hw RF FF HO RH F & + + + + + + + + H--C- +04+-0-+0+—-Br He-O++Cre-Cr-C- +8 “ 2 ff a as + + F- F* 4 oF + + w Poo tt a at Br # L-bromobutare e-bromobutans Add 5 . 3s oust lays. tins =, Ese ane bs £ Race rp eee ng 7 - we would see thet the alternation in the case of l-bromebutanse i: a butans, and we would much more brium mixture of the two could spresenting the polarity fore Ho oF oF + + + + H+ -C+—-CG-4+C4+-C-+H —_ — + _— + + = + Rk FF Br # in which the alternation is better. The possibility of writing e number of fermulee for one substance is a Weakness of the theory. The other concept of the poler conditions within an or- + rant ne team $a Ane Bene molecule is that of ey rae its) a oF se o s 2. bo xh Ss 9 x 3 qT i @ ct te t parr S a & for o s et bam @ aus a”! aa, ¢ 24% qk snnliad 4 Soe te, ~ afias4 “, Lewis" in detail, when applied to ‘the bromobutanes requires that we ee eee eee ee eee ee 3. Lewis, "Valence and Structure of Atoms end Molecules Chem. Cat. Co. New York, 1622. : mixture. Sines any tréensformation of one bramobutens into the Cther must be a dissociation into butene and hyd irogen bromide of both l- end 3-bromobutane the factors which control the th the character of the equi- double bond of butene will determin librium mixture. In the electronic formula fer butene, we, oes ; ony ane ve \e ; g 5 : a i a a a ee oe \ 7’ /* / substituent of the latter ig hydrogen. The general recognition that alkyl groups are more positive than hydrogen means that the four electrons of the "double bond" must lie closer to C, than to 03. This displacement of electrone away from the eurface of the n which they lie in such non-polar con at a a ey ad & Q bon atom, as shown below. This theory, then, requires that when. hydregean bromide adds te bu- tene the bromine atom go te Ce, end the ie-bromopropane has besn found* 56 ; prepane, and thovgh several workers°?° have studied the transfor- y mation of iso- to tertiary butyl bromide, only Meyer end Muller’ +: ~~ # = 4, Kekule and Schro ak ts ade Voight, J. ém. Chem. Soc. 28, 6538 (1916) find that an equilibrium (70 - 80% tertiary) is established between the two isomers. 7, Mever and Miller, J. Prakt. Chem. 46, 182 (1892) ons existing [te gsen to have investigated the equilibrium condit between the primery end secondary forms. These investigators heated lebromobutane under a reflux in the presence of iron wire which had been corroded by bromins, but subsequent fractionetion showed that no change had taken place. They then repeated the: experiment leading in a gtrong current of hydrobrowic acid, but found again that there had been no rearrangement. Finaily, a portion of l-browobutane with a length of cerroded ivon wire wag esaled into w glass tube and heated on a water bath for seven hours, but, save for a little charring, the contents of the tube were vneltersd, The l-bromobutane used in this treating l-butanol, Fasten, b.p. 116 - 1179 with sodium bromide at and eyl research was the a development of a and é=-bromobutane., ‘ ixtures of 1i- some preliminary work with these substances, réaction rates of propyl and isopropyl bromides > ‘with silver nitrate solution were considerably different: discov- 9. Wichesel and leunold, ann. 379, 288 (1912) ered & similar ineguelity in the reaction rates of the butyl brou- of gilver nitrate solution, with various tex t tube, about $O wm. long by 25 mm, ered te preclude by evaporation. 10.79 ce. of approximately 0.20 n silver nitrates solution were next eddad to the tube from 6 calibrated pipette, and the mixtures agitated by means of # swall paddle whirling at a conetant rate for exactly three houre at a tempereture of 224 (maintained by a water bath around the tube.) After this period 4 a a7 a om a = + — a oh aod of esitation, the contents of the tube were quantitative trang- fered to & beaker, where the excess of silver nitrete wag titrated with etandard potassium ferric eluminum sulfete as sn indicator. Pure 2-bromebutane, when subjected to this treatment, reacts to the extent of 88 per- cent, l~browobutane to 3.8 percent, while mixtures of the two I, which is &@ con- tH ad & es cr oe fos | aad m ct a < % fed ted ab we Ps ‘4 bon] o & cal 9 o & Et rive be tte 5. fa Quad o ge piletion of the results of twenty-th ree analyses of miztures of | various and known compositions, Curve I is plotted, percent tot- él bromide by analysis ag ordinates against percent composition by weight ag abecissae. Strictly, a sufficient number of points wag not determined to indicste beyond question the character of = a & id the error of the experimental methods. One can, then, by 4 the 2id of this curve, read off the percentage composition o ent of 1-Broz l-bromobutens wee cauced to rearranges to 2-bromeabutane im 8x: gs ret ge ce a3 ft " 3% by heating two to 2298 tubes, be -nmm. in dleneter, and varying in length from 60 to 110 These tubes were suspended in the vapors of boiling benzcic acid, at 249°, é, fey 7. P. Paxter} had shown that less than tens wag formed efter 20 hours! heating A sealed tube, after having been heated the desired length of time in the vapor bath, was cools: d the Qs Xe wy "s ra bs? De pa] & & Ss 2 contents washed with water until neutral (for a certain pressure ae of hydrebromie acid had alwoet always been built up.) The lie guid was next dried by shaking with a swall quantity of anhy- arougs copper sulfate, after which the clear liquid was drawn in- to the Lunge pipstte, and was enalysed. Duplicate analyses were made of the contents of all tubes, and reasonable checks were invariably obtained. Tebie II gives the results of the vérious runs. Discussion and Conclusions From an average of the velocity constants for each ex- oesriment, Curve TI, nercentage of g-bromobutene ageinet tine of heating, is plotted. The agreement among the individual constants, though not very good, yet indicates thet the reaction is mono- molecular; a vary close @ resment would noi, of course, ba ex- alysis are numer- B= ocity constants of Exrerivents 6 and ¢ were not in- i cluded in the average, for the product of the first wae badiy = a * 2 rm en at se a gt rm sharred, white the time of heating of the second weg not a&ccur- we ig 0.089 from which the deviation ig ebout 32] percent. confirm this conclusion, nee WES Ty oy 6 grams of 2-b3 suré had been built up, and titration of the water With which the meterial wae washed with a standard base showed 1.1 percent dissociation inte hydrobromic acid, agsuming that any hydrogen Jone met have come from the breaking down of butyl bromide into ”" the result s of which follow: Et. of Seamed Percent tot- al bromide m nee a) he oe an fe oo Lv ft 2 oe b, orl c id CG or oo [83] on eS > © 5 = : ° s a . 2 Yet these values de not indicate that the secondary bromide has unds reons 3 oO oo a> a Bed LQ a pry we ry i. pe Ci sy + ce iv oD ct hat6 Ss 0 he "3 3 tad, vt te es ped 0] oy “ ae fm. ow wa & @ Ee Db “ mt, brown than the material of any other experime i é 63.5 - 0,.2° 24% 3 $0.2 - 93,0° 404 4 92,0 - 95° ef 5 déerk residue eg The distillation, ag with other fractionaétions during this. re- search, covld not be continued because of viclent ae istillation was carried out with the product of number & (Teble II), l-bromobutans which had been heated for 50 hours, end two of the fractions were analysed by the silver nitrate methods: Fraction Temperature Renee Approximate Percent é-bromo- (uncorrected) Quantity butane by enalysis 1. below &9.6° 25% 3F Ps 89.6 - $0,1° 40 96 3 90.1 - 91.2° 17% 4 S1.8 = 98,5° ag 5 brown residue 10g q Tn the case of Experiments & and 9, the dissociation inte $ hydrogen bromide was determined by titreting the weeh weter with 0,54 N sedium hydroxide solution; diseociations of 3.1 and 4.2 Cne particularly interesting experirent (number 2) was verformed for the purpose of determining if the rate of rearrange- ment wes in eye te ro Se i 2 4 ans oS fo] oes pe S ‘ ad a gt BY & wn i " ae 6 R Ey By wa rc i om 8 ~~ n i i a foe BY o. o J oO be ci] S > oe D a o z ort a oo 1] aa " be | Eg 33 = Fa Feed oe Ss 3 «st 3 3g ; o a B th ad a > my . od vt as Ba ae rt o Ce) 5 rs} & oS a iy oo fea a si Q BY rest Set or) - a a + 2 Sg + eo ee ae! + 2] oO os o at a cy a < a S be "5 > a) xh g S ® Py Bs oe tent i ; Be 3 i] Bs} gi 2 o o DB . o = 3 © 2 ° S 2 B o a fa Se be a S35 aa 2 “a B 2 o | G o i at be Re) “ et a a a ei 5 a (a) 42 & ae 8 Bo xB 2 Bes rw] . tt ioe] @ S rot ay s a4 oe Sena S SS fa fe a Ss + a7] + 2 &s 41 a 2 ry a “a ri oS w a] Sd Ds ic Sad tes - ay a BS + id Ss a — a2 = a a2 oO i) ge DS ot v @ a rt 4 Be ba Da fin sa) > BS <2 aan ‘ a cy + ag tt @& ao Sa 4 Be ed Be] y 4? + he q al 42 “4 we) he es 3 i) = 3 Ss Pe a oan S R en 13 real 3 . ct D> Pa 2 Es Q a By Rs) 4 G Oe s ed ss) @ 3 a ad a i cra ot fi 7 Sh we a 3 et @ i Ds o ; rt 3 ri oe o Sad me bo ap ed Sd avy Q bey be ef o & he Pont oie ci Sd : ie) Es ct ny) aa) fet Me De 8 8 re <4 a = 2 Bs ra x 4 > 4 9 Bs ‘ 3 ao ot ot & Pa “ Sh “rd = > cc srt ra 3 = ce de > a D 4 > 2 roi . a | - a ri ad ieee} it o cd DB ro) ci ay cae ad eo bet DQ 4 So ba . = a oa s Bd g g QD in 4? aa » Be ce 5S oO > a a 7? uit fo i Ba 2 Q a a co Sea 2 a ao a ke Sa gq at 2 ie 3S co 42 Py ork Do Ga ol ua 2 Se ra 2 iw a Q Eos 2 o wo SS ad & a8 D 3] +s > ri a o o bP i) “4 D2 2 ~ s GG be i] Sd “st ad Sd a o rt a NY} a5 a vi "S Be ot al xl . ot ~~ a a BS) 4 A ] a 23 ge w eB ay om tee 42 S <2] S 2 a Ke 42 Ba) "3 + S ad fet + St aa D bs oO teat o Ey ad 0 ee » ot ad - oO Bt o a) & 3 4 Bs a a co as o ra i X Bi] 2 he & & a - os = = xv ad > 2 set Bx} Ee xa s s we “ ayy aa Qs a st wi - Sd ort ray " ihe eet . © 3 ban ” oe] i ot g] ri + “i a> S FS] ved x S09 3 = tz 2D ° =f ros) me & ci fy D 4 oO a Sd Fad et s © Ss oe Be “ct a D Es 2p Pay ~” at ba] oO - od a 3 ae) ra n Bc re} fe 2 “ 4 & av Sa voi “4 me aoa os + 2 S aa ao co co) D Fad 2 + reed ed ae 4 a * w 2 oe4 - iy > a 2 Fa & x > aod 3 S 7 a ice] ey ot aN oO a} 3 Sea a ard fe See red 3 a o o FS ~ ° c 2 a 3 9 s a Sow i 5) "cl © ™ A g & a Sy a = ri = iy ~~ fe i at xy re] Eat = icy <i Py 3 Sa a od q Ds fe bea 3 we Se 44 i] sel Sd Se oO aa on We © Pd ra at xf in i] 9 oS G - 2 » ) 2 s oO But a Ww wi g we s 3 x @ a Pe) i ay aad “ot ia oO > 3 ita 2 AG o 2 i) ® Sot ot Se So et Sa @ I fa a o oS a eet a] fe mc a Es oe G et ba oS Sew 3 ae ww 4 oO Es a cond a £4 a a ~— P| + Pt Ca eos fd ca) = O ha £ " & ie ‘cs a ws S = et @ a @ a ms] Bt es & om 3] caf a ort a oO @ as cS ci e Q “ct a <3 i . rt > 3 D be Fe} oo Sed & pa a 42 a st ' > gy bag cd ; 2 Ey . mt st ae a eH Fed 3 es ss - ed wet a fey wz w a tS) 2] rt ot fa on o Su xB Seat wed oO oa fo Bea pe ot ; rc + bard D2 co) fou] so] a 3 D> Re 3 + ee ° st E- ge Be Be & > Be S ct Bs] xa} ci fo « o a "g ort el - o e4 & a be > an o de a] + =} “et 2 S Sint o ® o 2 ra) <= 3 Sow a D a Sat ra Pa a ot 4 rt es * So sl & oA oD am a ro) G wi i By xX a 43 i} ag o ca 3 Ps 3 ss 3 so Py a xt i 4 “4 ri B +“ a wD ag a 3 co] ri re) Ret 4 we o Fae So cd @ 49 4 ort 3 G or Al ei s et 2 o 7 ‘i By ++ + a] a fas rr a a gS ; a ed res o we <3 2 a xs. te wa ri s Pet aor 2 oe wi i Es) Ny we 2 eo o a o De 4 > S 8 oOo 6 o fe - Ses + 44 3 ry ss ++ + ah & a a Pe m RN w ae » S a tet Fa ot ae @ “ cs) g cs) ci) oS ba} a 63 aS oS 5A m oD Et tes ot ra} oO a oa) > a < al o _ “ = et a re) es - oa 2 Dd a oo S o TH Oo oS 4 D Pa as 2 8 fs) ro Suummée. vy 2% a s . ry i) A method of determining 2-bromebutane in the presence of l-bromobutans has been developed. ii i- and Z-browobutane were heated separately in sealed o. tubes at 248 Swen rE aii romobutene rearranges compls 2-brome . am . . . . * at 248°, mobutane, save for « Little charring, remeine uneltered, iv) The rearrangement of l-bromobutane to 2-bromobutane is better exolained by the electron displacement theory than by BS ‘ the alternate polerity theory Oo wd § bend OG rd p zZ bere ' po oe Bpoj, ol we) ©] GP er] we] ay ef] a] oO} wm] oe) al al ae) of & ol w a . ry . ° . ° ° 2s ° ° ° o e ° ° e ° e o » a ° = 4 Ww z > <p cat) OD ae] a C3 en 2 o> ‘oo oy ut} ~~ rv) oP] ff ed > vy oe ed ta ee 22 cil rail] ce] we] wo] oO] SF] ef] es] wml] @e] wl] ml inl ~] =] wo] wow] ge < 3 Zetr{ |e] @|] of &] ale} o] @] ee} e | OO] wm] wl] CO] @] SO] B| w] of wy) © S -~ Oo ov © © coe) ol =f So oO ey Qo mm ‘or wy ~ i oe avy OO eg oD st oo CEST ole | el | ol «| ml[ wml +] al ole [a] Of ew] Of | cdf rit | alm! o 2 } et ri ot ri ot ri r4 rd ei] ei ot ra ci ot rt m4 et ool ri ot cl rt ° ohm > pl al | of af] a| oO] ao] wl] ol ss] @) a] Oo) es) OF] el Ol oO] ml] my, © Pa a 4 ra) Q co ao QO aa OQ O|] Ga] © a a oe Oo] a o co m2 oOo G Lad el © eSealal ol of e| co] ao] of ae] Go] ©] oO] GO| &| GO| oO] OC] SG] BG] GO] a] wo! 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Pencews Pesce] Kor SAMPLE STAL le-BROM- _ No. licarep fraxew ror [o2049 N joesis N BROWNIE | ANE eat Remarks awarsts | AcNO, | KSCN [Anatysis | Founn | REACTION 0.105 |20.0 |21.24|21.5 {22 1] 3 0.101 |10.0 |21.28]22.9 |24 [po3e ter heat- 0.074 |10.0 |21.80}21.4 |223 fae, Lid. had. eewe eure a e e 4! . face as b. Same quanti- 2 0.051 {10.0 ]21.58/20.2 22 ty of lig. in all tubes. [02204 [20-0 [22.47 ]29.0 |298 recline tube b hed. 2 : , sO 0.094 10.0 [21.62 \15.2 [20 [hear | times, the free volune 0.096 |10.0 |22.49/20.4 }22 Liguid colorless. | tube Cc — a . aga, but 3 tines the 0.094 ]10.0 |21.52/20.4 {21 L liq. surface of g and b.| 0.106 |10.0 ]19.74/38.5 }44 317 0.098 10.0 }19.84}40.5 147 |}.037 O.128 [10.0 ]17.66/52. |62 4 |19 0.101 ]10.0 |18.58/54. |64 17023 ©.108 10.0 }18.40/53. |63 5 120 0.112 [10.0 |18.05/54.8 |65 |).022 6.118 {10.0 |16.17/50.8 |60 The liquid in this 6 j27 tube was very dark 6.080 ]10.0 ]19.512154.5 | 65 :— brown after heating. . Very little free volune 7 l29 0.081 [20.0 |i7.e2/ 71. | 86 in tube during heating. The anélysis was con- 0,091 ]10.0 17.65/72. [89 |}031 | firmed by fractionaticn. ~ Dissociation during heat 2 3 3 leo 0.092 }10.1 |17.32179.5 |97 ing determined by titre- 0.067 [10.0 J1s.77}7e.5 j96 |ho2zs | 29H, ERT in gash Katey 0,097 |10.0 116.66) 80.8 |98 Exact time of heating um S$ |80 known. Dissociation de- - |c.094 ]10.0 |16.e5/80.e |98 |}021 | termined as above: 4.2% Percent 2-Bromobutane Formed 90 80 70 60 50 40 30 20 10 CURVE I1 Rearrangement of 1~Promobutane at 248° Lo q op y 0 10 20 30 40 50 60 70 80 90 Time of Heating in Hours