PREPARATION AND PURIFICATION OF AN ALKYL HALIDE C.M. C ABRERA ABRERA 1 AND J.J. CHUA HUA 1 DEPARTMENT DEPARTMENT OF FOOD SCIENCE AND NUTRITION NUTRITION,, COLLEGE OF HOME ECONOMICS UNIVERSITY OF THE PHILIPPINES, DILIMAN, DILIMAN, QUEZON CITY 1101, PHILIPPINES DATE PERFORMED: 25 JUNE 2015
ABSTRACT
This pape ai!s "# $es%i&e "he !e"h#$ #' pepaa"i#( #' tert)&*"+ %h#i$e, a( a-+ hai$e, "h#*.h tert-&*"+ a%#h# a($ %#(%e("a"e$ h+$#%h#i% a%i$, "he !e%ha(is! #' "he ea%"i#( "ha" is "a-i(. pa%e $*i(. "he s+("hesis, a($ "he p*i p*i/% /%a" a"i# i#( ( !e"h !e"h#$ #$ #' $is" $is"i ia a"i "i#( #( "# a%* a%*i ie e a p*e p*e p#$* p#$*%" %" The The sai$ sai$ #&2e%"i3es ae a""ai(e$ &+ "he i("e.a"i#( #' "he a*"h#4s %*e(" -(#5e$.e e.a$i(. "he s"*$+ #' Rea%"i#(s #' A-+ Hai$es a($ #.a(i% s+("hesis, 5hi%h se3 se3es es as a( app appi% i%a" a"i# i#( ( #' "his "his -( -(#5 #5e$. e$.e e Th# Th#*. *.h h *se *se #' a sepa sepaa" a"i# i#( ( "e%h(i*e "ha" i(3#3es "he sepaa"#+ '*((e, "he S N 1 !e%ha(is! "a-i(. pa%e, a($ e6p#s*e e6p#s*e "# a si!pe si!pe $is"ia $is"ia"i# "i#( ( se"*p, se"*p, 07 !L #' tert-&*"+ %h#i$e 5as #&"ai(e$ '#! 100 !L tert-&*"+ a%#h# a%#h# 8i"h 8i"h espe%" espe%" "# "he s"#i%hi#!e"+ s"#i%hi#!e"+ #' "he #3ea ea%"i#(, "he pe%e(" +ie$ is 9:1;<
INTRODUCTION
During Post World Wr !" t#e need o$ tre%endo tre%endous us %o %ounts unts o$ resour&es resour&es'' t#ese rnging $ro% $ood nd guns" to tolue toluene ne nd gl(&e gl(&erol rol $or indust industri rill l)ortor( use re *ides+red o,er t#e t#e e& e&te ted d &o &oun untr trie iess .1/ .1/ As n ns*er to t#e gro*ing ne&essities o$ t#e t#e +o +o+u +ul lti tion ons" s" t#e t#e s(nt s(nt#e #esi siss o$ orgni& orgni& &o%+ &o%+ound oundss *s de,elo+e de,elo+ed d T#e s(nt#esis o$ n( orgni& &o%+ound reuires t#e &&o%+lis#%ent &&o%+lis#%ent o$ t#e $r%e*or o$ t#e desired desired %ole&ule %ole&ule"" introdu& introdu&tion tion"" trns$or%tion or re%o,l o$ $un&tionl grou+s" e3er&ising sele&ti,e sele&ti,e stereo&o stereo&ontro ntrol" l" +rodu&ti +rodu&tion on o$ reson)le %ount o$ +ure +rodu&ts nd ting into &&ount t#e e&on e& ono% o%i& i&l l s+e s+e&t &t o$ t#e t#e +ro& +ro&es esss .2/ .2/ E E&# &# s+e s+e&t &t o$ t#e t#e +ro& +ro&es esss is $urt#er %de ei&ient' llo*ing t#e s(nt#esis o$ orgni& &o%+ounds n i%+ortnt i%+ortnt $or% o$ e3+eri%e e3+eri%entt nttion' ion'
)ot# in t#e industril nd do%esti& s+e&ts T#e +re+rtion nd +uri4&tion o$ "e"))u )ut( t(ll &# &#lo lori ride de 67896l is +reli%inr( tril nd ste++ing stone to understn understnd d t#e )si& %e&#ni&s %e&#ni&s o$ t#e s(nt#esis o$ l(l #lides" in t#e %i&ro l)ortor( setting Follo ollo*i *ing ng t#e t#e trn trns$ s$or or% %ti tion on or re%o, re%o,ll o$ $un&ti $un&tion onl l grou+s grou+s"" t#e generl ,ie* o$ t#e +ro&ess is t#e &on,ersion o$ tertir( l&o#ol to &orres+onding #lide )( re&tion *it# #(dro#logen #(dro#logen &ids" ll under under t#e ;N1 %e %e&# &#n nis is% % .
t#e (ielding o$ t#e desired +rodu&t" "e"))ut(l &#loride" is s $ollo*s: .7/
T#e i% o$ t#is e3+eri%enttion is to s(nt#esi=e &rude tert-)ut(l &#loride $ro% t#e re&tions o$ t#e tertir( l&o#ol tert-)ut(l l&o#ol nd &on&entrted #(dro&#lori& &id nd to &uire +ure +rodu&t )( using si%+le distilltion setu+ METHODOLOGY
As %entioned )o,e" t#e +re+rtion o$ t#e Al(l 8lide "e"-)ut(l &#loride *ould reuire t*o dierent regents $or s(nt#esis" n%el(" tert)ut(l l&o#ol nd #(dro&#lori& &id !n ddition to t#ese regents" sodiu% &#loride N6l solution" sodiu% )i&r)onte N86O <" nd n#(drous 6l&iu% &#loride 66l 2 re lso used in t#e e3+eri%ent to id t#e $or%tion o$ "e"-)ut(l &#loride T#e t*o %in regents" "e"-)ut(l l&o#ol nd &old &on&entrted #(dro&#lori& &id" *ere 4rst dded toget#er into se+rtor( $unnel in 10:20 %> rtio res+e&ti,el( T#e $unnel *s t#en s*irled gentl( )( using stirring rod A$ter *#i&#" t#e solution *s le$t to stnd in order $or t#e l(ers to settle < %> ? M N6l solution *s dded into t#e $unnel to $&ilitte t#e se+rtion o$ t#e t*o l(ers A$ter t#e t*o l(ers #,e $or%ed" $e* dro+s o$ *ter *ere dded into t#e $unnel to deter%ine *#i&# l(er is t#e ueous l(er" noting t#t t#e *ter s#ould dissol,e in it T#e deter%ined ueous l(er *s re%o,ed $ro% t#e $unnel &re$ull(" nd *s dis&rded T#e orgni& l(er on t#e ot#er #nd *s trns$erred into dr( @s *it# sodiu% )i&r)onte T#is %i3ture *s gentl( s*irled to %i3" nd *s
de&nted into not#er dr( @s' *#ere it *s treted *it# n#(drous &l&iu% &#loride $or desi&&tion T#e indi&tor )( *#i&# t#e "e"-)ut(l &#loride s#ould )e de&nted into round )otto% @s $or t#e ne3t +#se o$ t#e e3+eri%ent is *#en t#e &l&iu% &#loride &lu%+s toget#er On&e de&nted into 25-%> round )otto% @s" )oiling &#i+s *ere dded into t#e solution" nd *s distilled t#roug# si%+le distilltion set-u+ T#e solution t#t )oiled t te%+ertures round 79-526 *s &olle&ted into @s in n i&e )t# T#e distillte *s %esured t#roug# grduted &(linder to get t#e ,olu%e' ste+ ,itl to t#e deter%intion o$ t#e (ield A$ter*rds" solu)ilit( test *it# distilled *ter *s done to identi$( *#et#er t#e &uired +rodu&t is +ure RESULTS AND DISCUSSION
T#e $ore%entioned %et#odolog( *s done to ttin t#e gols o$ t#e e3+eri%enttion: to s(nt#esi=e nd +uri$( t#e l(l #lide" "e"))ut(l &#loride T#e generl o,er,ie* o$ t#e nu&leo+#ili& su)stitution re&tion )et*een "e"))ut(l l&o#ol nd #(dro&#lori& &id is s $ollo*s:
Fig. 1. Nu&leo+#ili& ;u)stitution Re&tion o$ "e"))utnol nd 8(dro&#lori& &id
T#e s(nt#esis o$ "e"-)ut(l &#loride in,ol,es series o$ ele%entr( ste+s" *#i&# &onstitute t#e !e%ha(is! o$ t#e re&tion ;in&e t#e re&tion +ro&eeds in n ; N1 $s#ion .5/" t#e %e&#nis% is t*o$old: t#e loss o$ t#e ea3i(. .#*p to $or% &r)o&tion nd t#e nu&leo+#ili& tt& $ro% eit#er $&e o$ t#e @t &r)o&tion .?/ T#e %e&#nis% strts u+on ddition o$
e3&ess &old 86l to "e"))utnol 86l is &ooled )e$ore ddition due to t#e ,oltilit( o$ t#e ot#er regents' +#se &#nge *ill t%+er *it# t#e &on&entrtion o$ t#e regents nd to t#e (ield o$ t#e e3+eri%ent
T#e +ositi,e &#rge o$ t#e &r)o&tion %de it sus&e+ti)le to nu&leo+#ili& tt&" *#i&# results to t#e nture o$ orgni& re&tions' t#e inter&tion o$ ele&tro+#iles nd nu&leo+#iles T#e ttr&tion )et*een t#e o++osing &#rges )rings )out t#e $or%tion o$ "e") )u(l &#loride
Fig. 2. Mo,e%ent o$ ele&trons nd
Protontion
T#e re&tion )o,e is )si&ll( n &id-)se re&tion T#e strongl( &idi& &#r&ter o$ 86l %de it &t s Bronsted->o*r( &id' t#ere$ore +rotontes t#e O8 - tt&#ed to t#e "e"))utnol T#e trns$er o$ ele&trons resulted in t#e )ond )rege o$ t#e 8-6l )ond nd $or%ed t#e O-8 )ond t t#e side o$ t#e "e"-)utnol T#e O8- is no* ssigned s t#e le,ing grou+" nd t#e ti%e )( *#i&# t#is tes +l&e deter%ines t#e rte o$ t#e re&tion Alt#oug# dding 86l *ill not in&rese t#e rte o$ t#e re&tion" it ensures t#t ll "e"-)utnol re re&ted to $or% t#e desired +rodu&t .C/
Fig. 5. Redu&tion o$ sol,tion o$ tert-)ut(l
&#loride t#roug# dieren&es in +olrities
B( t#is ti%e" n e%ulsion o$ t#e *ter-insolu)le +rodu&e" "e"-)ut(l &#loride nd e3&ess 86l is +resent in t#e se+rtor( $unnel T#e +ronoun&ed se+rtion o$ l(ers is $&ilitted )( ddition o$ t#e sturted N6l solution" +ro&ess t#t is re$erred to s slting-out .G/ ;in&e t#ere re ions t#t re introdu&ed" t#e dieren&es in +olrit( *ill )e %ore e,ident' t#us" %ore distin&t l(ers Fig. 6. Re&tion o$ ;odiu% )i&r)onte nd
8(dro&#lori& A&id
Fig. 3. Trnsition ;tte
T#e genertion o$ +ositi,e &#rges )roug#t )out )( +rotontion o$ t#e O8- grou+ introdu&ed t#e #ig#est energ(" *it# res+e&t to t#e re&tnts nd +rodu&tst#e trnsition stte T#is +rt o$ t#e %e&#nis% is lest st)le !t leds to t#e $or%tion o$ t#e &r)o&tion nd *ter
Fig. 4. For%tion o$ desired +rodu&t
Addition o$ solid ;odiu% )i&r)onte re&ts *it# e3&ess &on&entrted 86l in n &id-)se neutrli=tion re&tion T#e slt is dded in solid $or% due to t#e i% o$ desi&&tion !$ ueous sodiu% )i&r)onte is used" %ore *ter *ill )e introdu&ed to t#e set-u+ On&e t#e re&tion )o,e #s ten +l&e" n#(drous 66l 2 t#t *s dded ne3t *ill dr( solution u+ o$ *ter ;in&e it is seen in t#e generl re&tion Fig 1 t#t *ter is in t#e +rodu&ts side" introdu&tion o$ *ter genertes t#e $or%tion o$ t#e regents" *#i&# is not $,or)le $or t#is e3+eri%ent >e 6#HtelierIs Prin&i+le re,erses t#e euili)riu% to*rds t#e $or%tion o$ regents *#i&# *ill lo*er t#e (ield o$ t#e e3+eri%ent .5/
insolu)ilit( o$ "e"-)ut(l &#loride in *ter
Fig. 7. For%tion o$ iso)ut(lene
Alt#oug# it is onl( in s%ll +ortions" i$ +resent" t#e regents o$ t#e e3+eri%ent %( re&t in dierent *(' t#e $or%tion o$ t#e lene" is#&*"+e(e" is +lusi)le As #(dro&r)on t#t is gseous in roo% te%+erture" it is +resu%ed t#t iso)ut(lene is lred( e3+elled out o$ t#e se+rtor( $unnel during t#e s*irling &tions .5/ T#is $or%tion *ill t%+er *it# t#e (ield o$ t#e e3+eri%ent On&e t#e ueous l(er #s )een 4ltered out" t#e orgni& l(er *s su)e&ted to distilltion T#roug# distilltion" *#ere sele&ti,it( $or t#e $r&tion t *#i&# t#e s+e&ies t &ertin te%+erture t#t is *it#in t#e rnge o$ t#e )oiling +oint o$ t#e su)stn&e to )e isolted is +r&ti&ed" it &n )e ensured t#t t#e su)stn&e )eing &olle&ted t &ertin te%+erture is %inl( t#e tert-)ut(l &#loride T#is is &ertin due to t#e )oiling +oint o$ t#e sol,ent used is #ig#l( dierent *it# t#e desired +rodu&t T#roug# t#e distilltion +ro&ess" )oiling &#i+s *ere dded into t#e s%+le to %e t#e )oiling gentler' ensuring no dro+lets *ould go dire&tl( into t#e &ondenser !$ dro+s *ere to )e deli,ered to t#e &ondenser" i%+urities to t#e +rodu&t %ig#t o&&ur !n order to &#ie,e t#e %3i%u% (ield o$ t#e +uri4ed +rodu&t" &ontinuous *ter @o* %ust lso )e en$or&ed in order to #,e %3i%u% &ooling A$ter t#e distilltion +ro&ess" it is e3+e&ted t#t t#e distillte &uired is +urer t#n t#e orgni& l(er &uired $ro% t#e se+rtor( $unnel T#e distillte is lso dded to *ter to test its solu)ilit(" *#i&# turned out to )e i%%is&i)le T#is ste+ *ill so%e#o* ensure t#e +resen&e o$ *terinsolu)le &o%+ound' &onsidering t#e
A$ter t#e distilltion +ro&ess" t#e ,itl e3+eri%entl dt re ten into &&ount T)le 1 Table 1. Kolu%e nd Mss o$ t#e >i%iting
re&tnt nd +rodu&t t-Butyl
Volume, mL Mass, g
t-Butanol
chloride [experimental]
10.00 7.88
0.8000 0.808
Wit# res+e&t to t#e o,erll re&tion" t#e %ole reltions#i+ o$ t#e regents to t#e +rodu&ts is 1:1 T#is $&t i%+lies t#t t#e nu%)er o$ %oles o$ "e"))utnol s#ould )e eul to t#e (ielded "e")But(l &#loride A$ter &o%+uttion o$ stoi&#io%etr(" t#e $ollo*ing dt re &uired: Table 2. E3+eri%entl nd T#eoreti&l
results
%%ol Mss" g Per&ent Lield
T#eoreti&l
E3+eri%ent l
10?7 9G79
C<57 0?G0G
?912
T#e +ossi)le resons $or lo* +er&ent (ield t#t t#e ut#ors suggest re t#e +ossi)le o,er+rodu&tion o$ iso)ut(lene nd t#e in&o%+lete desi&&tion o$ t#e s(ste% !t is lred( %entioned t#t t#e side-+rodu&t iso)ut(lene is deri,ed $ro% t#e regents t#t *ere used in t#e s(nt#esis" *#i&# %ens t#t *it# res+e&t to t#e &on&entrtion o$ t#e regents used" t#ere *ill )e dro+ in t#e +er&ent (ield T#is &n lso )e #eld true $or t#e in&o%+lete desi&&tion E3&ess *ter *ill re,erse t#e euili)riu% +ro&ess to t#e le$t" *#i&# is t#e $or%tion o$ t#e regents SUMMARY AND CONCLUSIONS
!n &on&lusion" t#e s(nt#esis o$ "e")ut(l &#loride t#roug# nu&leo+#ili&
su)stitution )( t#e ; N1 %e&#nis% "e"-)ut(l $ro% l&o#ol nd #(dro&#lori& &id *s su&&ess$ul" #o*e,er t#e +er&ent (ield +resented to )e gretl( )elo* t#e t#eoreti&l (ield &o%+uted" $lling t onl( ?912 out o$ t#e idel 100" or onl( 0?G0G g out o$ t#e t#eoreti&l 9G79 g T#e lo* (ield %( )e due to t#e +rodu&tion o$ t#e side +rodu&t" iso)ut(lene" or t#e e3&ess o$ *ter in t#e s(ste% *#i&# %( #,e &use t#e re&tion to %o,e in )&*rd %nner &on,erting t#e "e"-)ut(l &#loride )& to "e"-)ut(l l&o#ol 8o*e,er" des+ite t#e lo* (ield t#e &o%+ound +rodu&ed de%onstrted #ig# +urit( s it $ul4lls one o$ t#e &#r&teristi&s o$ +ure "e"-)ut(l &#loride *it# regrd to its i%%is&i)ilit( in *ter REFERENCES
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#tt+:***%sterorgni&&#e%istr( &o%20120C1<t#e-sn1-%e&#nis% .7/ ;(nt#esis o$ t-But(l 6#loride $ro% t-Butnol nd Retrie,ed June 29" 2015" $ro% 6le%son Uni,ersit(: ***&le%sonedu&es&#e%istr(org ni&>)sBut(l6#loride+d$ .5/ T#e Uni,ersit( o$ !llinois nd Pre+rtion o$ t-)ut(l &#loride .PDF/ Retrie,ed on 29 June 2015 $ro% #tt+:r&#i,esli)rr(illinoiseduere &Uni,ersit( 20Ar&#i,es15050506#e%2<7old >e&turesPDFtBu6l+d$ .?/ onig" B 201< ;(nt#esis o$ 2&#loro-2-%et#(l+ro+ne tert-)ut(l &#loride $ro% tert-)utnol .PDF/ Retrie,ed on 29 June 2015 $ro% #tt+:***o&+rtiu%deno+eninstru&tions+d $702?Qen+d$ .C/ 6li$orni ;tte Uni,ersit( nd E3tr&tion .PDF/ Retrie,ed 29 June 2015 $ro% #tt+:&#e%istr(&sud#edu$&ult(no el68E<1C>E3tr&tion 20E3+eri%ent#t% .G/ >ong !slnd Uni,ersit( nd E3+eri%ent <: Pre+rtion o$ tert)ut(l &#loride .PDF/ Retrie,ed 29" June 2015 $ro% #tt+:%(*e))rool(nliuedus*ts on;ite>)ortor(QMnulsQ4lesE3 +<+d$
