Stereochemical Relationships of the Isomeric 3 Chloro 2 Butanols and the 2,-3-Dichlorobutanes Citation Gould, Clark Webster, Jr. (1940) Stereochemical Relationships of the Isomeric 3 Chloro 2 Butanols and the 2,-3-Dichlorobutanes. Master's thesis, California Institute of Technology. doi:10.7907/px28-mz96. https://resolver.caltech.edu/CaltechTHESIS:12082024-135314029 Abstract No abstract. Item Type: Thesis (Master's thesis) Subject Keywords: (Chemistry) Degree Grantor: California Institute of Technology Division: Chemistry and Chemical Engineering Major Option: Chemistry Thesis Availability: Public (worldwide access) Research Advisor(s): Lucas, Howard J. Thesis Committee: Unknown, Unknown Defense Date: 1 June 1940 Record Number: CaltechTHESIS:12082024-135314029 Persistent URL: https://resolver.caltech.edu/CaltechTHESIS:12082024-135314029 DOI: 10.7907/px28-mz96 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 16909 Collection: CaltechTHESIS Deposited By: Benjamin Perez Deposited On: 11 Dec 2024 18:28 Last Modified: 11 Dec 2024 18:30 Thesis Files PDF - Final Version See Usage Policy. 8MB Repository Staff Only: item control page

3 Chloro 2 but,anol z ~u1.cl t11e 2 , ... 3 ... pic11lorobu-t.aiies • .in p a rti al :f'ulfilmcn:t of t.hce :r.equire:me:nts Ca J.if'o rnia Institute of Teebnology Pasadena, Cali:f'or..nia June , 1S40 Irrt;voductory : hyd.rin yielded the dl d.i.br ,,t;Li.de . hyd:coch lo:r'ic a c id to give tirn meso dic hlo:r·i d e? chlo:c·ic D.cid to give onlJ traces oi' dichlo:c id e, s.:o t,'lJ.:x t an exact In order to :t:'olltiw t he storeomut,u:tioI:.s \·,hi c1:i. accoruranied but anes . propertJ.es. c./ / C H.s =C "H Gis 2-butene H I I C, H - C. - C - C H 3 3 I I H Cl H I C.I I + CH 1 -c-c-c..H 3 I I c. I H al 2,3-uichlorobutane And: Trans 2-bi;tene mesa 2,3-dichlorobutane !'hes~i f\nmulatio:ns assu:c1e t,rans additi ""11 o:f the halogen t,o t11e ole• activity. difi'icu.lty • Yields ·were tion of tri- and tetrc1-cl1lorob .:ctanc0s tc) tlH;: ext.e:n:t oi' 5-10 'ri . 0 ,2 '£he dichlorides v:c:r'e dif.::t:Llled t1n"oti,sJ1 a 1.1:0 crn. Weston Configw:·ation dl .t) .p. /7 ~10 •r· 117 .1° c. 1.4386 1.4400 1.10G4 ,"').,:: com.lenser read:i.:r;i;;,:,..., 3 CtefJC::r,; J..l:;ed 1;11~evi. c> ~~GJ.}/. Si :ncG in t his cel.l t.lw c 01h5.e1.wer· benzene, et:t1,rl bro:.:iide and ethylene <.Lic h:Lor.id e. the: Le c :;~lib:.:•atiJ1g' .subst,m:i.ces a:r·c 5iven elsevlhe:;:•ef The c u:nst:::ul'i:,s for I 3 Chloro 2 butancls HCI H . Cl I I CH 3 -C-C-CH 3 + I I Cl I-I I I CH3 - C-C. -cH I rOI-I H I I C H 3 -C- C -GH 3 I H I H 3 HOH OH C/ He/ , I Cl OH I I I I 1--1 H + c. H3 - C..- c. - c,,1-, . 2. Aft.c;c 3 -:i.,(r.,ti.l.L,;.t,.L z.n1ctlu"ol,tgi1 the Wes ton colwm1, the ~.:. cL.loro 3 t.hreo trans 52 . 0° 0 c. 1 . 4387 0 91. t/ - f'Z-1 C ui:.;S"umptton vd.11 be tested in the futu:r-e . HC l a:nd HCl + Zn.Cl 2 : :t.Io di c h lo1· i d e p h -: .. ce w:-'.s i \ >:rI:::.Hed. '{ c. coul6 not be dlc tilled . dibutyl ether 'WO.S 'I'he e:r;•y thx·o ch1orohydr .,_n v~t 1s aCded. to a 'J.lhe dic h lo:i:•ide to a dichloride dl dichlo:ci.de . took pJ.Lice with ei th.er o o:.."" 2 wc~lden Inversiorn3 . o f t h e hig'h lJoi lin g d i c hloride pr- ep,'1x·0d i'r oJT1 the vu re cis 2 - bu tene , t h e moso i somer. OfJt i.c all;,/ ucti ve eryth:ro cl1lorohy c.h--~u1s to d ichlor i d e . ~ \;eJ;l cr 1 s methc,d , pu.r t :Lal a.c et d 1ati on oi' t he a lcohol :Ln t.h o Th i e, c hloride v:a,";. t.hcre:for- e t Liu:ny1 c hlor i d e a:n.d , :n;·id.:ine . " . t ,••, •"' D • J.1 •/ dV ·- .z 5' (f ( l d c m) The c J. isomer h as a higb.c:r dieJe c u•ic c on c t a nt, than the meso . For the 2 , -:3, d.l.bi•omob"tJ.t ~m<:is , i t is i.',l,1e m.e;;;o for m 6 I i:u tho r..'.LLch.Lo1·:Lde s likewi~H.3 :restri ct rotation ar ounci t.:he C;a - Cs This bon~\ , but t:h.:t tb.e ch1or:Lncs t.J:1Ennee lvcs lie c:i.s to eacL o tllE>.r· , m1n:ht exr,;. ~ , lai.n tJ:10 fa.ct tha.t Fo:crnul atiri£; the 11e Cdl > li'i0S t:.. O :tor . • .,.\.... ,. t1 =cl1lo:r-o butqne r, .J.. · ~ . carric:d • • • . _; . •. ;.:; • i n the: chlo:rinc:tion oi' t he 3 c t.lo:i:·o 2 but anols: H H I C H3 ~ C - C I I I Cl I H-C-OH HO-C- H I +C 1-CI - ,__, I I CH 3 CH 3 ~ H -C-c1 e rvtnro c :" J orc,•r -;:;:- i n ,j - C H3 CH 3 I I I H-C-CI + I H-C-CI I H-C -cl c1-C- H I + I CI - c-H f-1-C-C I I I CH 3 CH 3 CH3 \. _./ ,..___----...r- Cl CH3 CH 3 I CH~ c H3 y-'"" dl r: ·e G 0 ,,, :•1 ixt 1.i re CH3 Cl-/3 I I H - C- CI I Cl -C- H I CH 3 + CI -c-H I H -c-c1 I CH 3 / H H I I CH3-C-C-CH I I Cl Cl Cl H I t 3 H H I C H3 - C- C - c,.. H I I 3 I · OH Cl (+ ) er·t:1 ro .c 1-·c-rC'r1 :rc:ri n CH3-C-C-CH ' Cl' 3 H \ - ) d i c 0·: J u :r i (: e H I -C-01--J I CH 3 '1 H d - r,b e r ·' J:, et t y 1 c ar:) i. r: o J. • I C-CH I 3 Cl l - l''' eriyJ r: e t r~y 1 ch 1 c·rcJ•·e tl 1 an e • ft c., f-1 I C - 01-1 I COOCzHs- I 0 -c- H I C 00 C 2. H:,- ·~ ~'. yJ }J n e ny lc ►J J.o r n 1:tc eta te H I ¢ - C- Cl I cooc~ Hs d - erhyl jJ/?~.nyle1~/cro llC elare -lo- is irrtcrcsting to :note that / '1 H H I I C - oH C{, H ,3 - C~ H13 - \ C - Cf---13 I CH c, 3 J d -foct ano l ---, ·~ .. .. ~. f c:-1J.o rooct2 n,;: 10 ' 1~11.i ..LJ. ..L I~.! fi bon. ren0rnble the /3 oct,.2.nol. 0 y- i s involved ii:1 the :r•e:r1c ti.on ·tiu:~eo chlorol:qclt·in ~::: , :3 ... SOCl2 ➔ dl dichlo:ride, t.u:t.cuJ.edi o 1, II des-er Lbed. II The dl 2, -3-dicL10:robut:-:.1.J1e: :r•eactor The cis ~~ -butene was dist.U..1cd out, of' t,he the bubble r.ig:ht -::-.. . into the ren.ct;:.,r, T11e@cLJ. ori:n.e reaetl 011 ole~f:Ln o.nd h:J.J.og~n. ~ ~ ~ ..7 / a"do../d~/ ,,ovo ,,;J.J/ l?../(7 ../dlt;/.,I I \i ~ ~ ~ r\j ~ ~\) ~ \J~ ~ ~ b ~ ~ ~ '~ ~ ~ ~ ~ . ~ ~ ~ ~~ ~~ \3 ----.:1 ===ail] ~ 1~ ~ ~ ~ ~ e£ ~ diotillat,J.ons. Th€ e~i:perime:ntal procec.1.ure is the sa.rfre as that given above :fo;r tho prcpurat.io:r... of the dl dichloride. was then al.lowed to stir for 40 ;;:1inutes more. T'he s olid was washed with iso:propyl ~tJ;1.{W ea.ch, oi' i s opropyl ethe:r. corn.bined, d:cied of gle.ss helices, und t.oto.l rc:f'1ux J.ietillD.:t:t.o:n head., 181 g. of The This n.t.'.-\tcri.al wo. u rcd:Lstilled three times tlu... ough the Weston coli.-1. li.u:i. , 86 of 79 Tl.1c:: mixtu.re was kept at the:1.t \'ii t.J.1 The chlorofoi•.m solutJ..on 'ivao c ooled, wushecl/5 £mcces$ive 70-73 ° C. at 30 m:m. ··)._r• .read:u:,.g.s i.:-tcr-e good \Ni tLLin .:t 0 . 01° , -'• ·• Q •v<=Q<) ip , n/ V\ 26( D 1 ,'1 r•D·),.,...,.__1 0·f' _ ... ~ ~ 0 (1 d.cm) of chlorrJ1v·c.:r•.Ln ,:, n ,:,.;. ~" '"_- r~ ":I ''.:!'70 • ..,.., .... v~• "" ,.. ._., ••- - · 'I1he acW.i t:Lon took 35 rninu.t.en . ·which '.l'he f i l tro:te • m1 ef'f'icient coJ:u.xru1, t...11.en cooled, and 1uore PCl5 filtered ot"f .• .-.. '•Ol"V""l ~.'1..i., .\£1 ."'Z;~ W -\- i.. 1 0. - ~ "",;;. ,,,··n . •- :r'>v . ·~~ .£ ~ V 1 1 b.· uv . ,.~ "' ·1at·· t'b"'I} tll.G ~ i< -f•• t.,_J;;..,J....-;._. . ~ oti. , . C•<m··r_"i . ... tl:: 0 •l,: Ji,,. _. . " boil0"'' :t··e .•Bidue ~ • - • • Tho addition t ook 80 :minu:teo . dried The dichlor:lde Wi'.~.::1 :i:·eclii::-tilJ.,:.:: d tvrice, b .• p. 4 f>.O .. 4D.6 at 80 ta:a, 25 n.l) ;::;: 1.4392 , c c):U(usncer i·eadillf.;; 1G1.4. 1'.hp ,1t 49.4 • 49.? at SO mm., n:o 9C. 0 ::= 1 .. 4386, c oncle:nser l"Cl:).d;ill.§ _:;.64•0, chlo:cide. Stirring v;as c o:n:t:Lnued for 20 minutes after· I~t.·tcr 2ta:o..ding overnigl:J.t,, tb.e o5.l o:f d.ich.loride was collected, Yield 63 X, . had b.p. Ack:Jaenvledgm.Qnt.s: I am grateful to DINJ* V.'ood and Dickinson for v u luc;.ble asiSistall<;e in maki:ng vi~ dielectric constant. mearn.1r·ement$ , could not huve been qar·ried out. T1-.r.1e ste:r·eoche:..""tlea1 rela:ti ,>:rwh.ipe of the 3 c lllo-ro 2 but.anols and the 2,,3 dichloro'J::)trta.iles have been studied. Cl1lori11.c:tiol1. o:f the c:b.J.oi-•ohydriz.1 with thionyl chloi·ide procef:dS with z~.ro qr two VJalde11 inveJ?sionJ Ghlorination with t h:i.o:rzyl chloride a_n d ;pyi..idiJlQ involves one Walden Inversi0nf PCJ.f:> as a h,~1ogenatil?€ agent giv~s mi:)::tl.U'es of' dichlor•idesf and. hycb.:·Q(_l hlo:c:L<:: acid does 11ot react w.ith the chlor°"" The prope;r,t.ies of' t,he 2,3 d.ichlorides and 3 cllloro 2 buta.nols ai"e rtefert:nces W'instein and Lucas, J.A.•J.o. 61, 1576, 2 ;1 45 , West·on, Ind • .l!;ng. \Jhen. anal. _,:!_; d • .§., 179 , (1 9.3~) . \1~~3J. ''.'cc u a nd Dickinson, J.A. 1..;. 3 . 61, 3259, ll 939 ). Lucas, J.A.G.3. 52, ' 02 , (1 S' 30). Wegler, Ann. 506, 77, (1933). :Stevenson and Schomal<:: er, J.A.1..;.S. 61, :~173, (1 939 ). r,_enycn, P hilJ ir,s, et al., .., • Ghern. '.-:ioc. 1931, 3112. Kenyon, ''hi lJi r s and L i pscc:rro e, ibid 19::z,r,, 415. I ever,e and .< iJ.ikeska , J. .'!i.C.Kenzie Dnd Tu dhope, b iol. \;hem. !:)S' , 45; tl9 24 ) • ibid. ,,2 , !:)51, (1S24J. F en:.ror and T'hi lli r s, Trans. ~'arctday ::-;o c. 26 , 4:J :l, (1£ 3 .J ). 'Y ilson a.nd Lucas, J .A.G.S. ~ ' 2:7-96, ----8---- {1 936 ).