DEPARTMENT OF PHYSICAL SCIENCES AND MATHEMATICS College of Arts and Sciences Uniersit! of t"e P"ili##ines$ Manila
CHEMISTRY 31 Course Title: Course Description:
Credit: General Objectie:
Ele%entar! Organic C"e%istr! St&d! of str&ct&re and no%enclat&re of si%#le organic co%#o&nds$ t"e conse' conse'&en &ences ces of str&ct str&ct&r &re e on t"e #"!sic #"!sical al #ro#e #ro#erti rties es and on t"e t"e reactions t"ese co%#o&nds co%%onl! &ndergo$ and t"e %ec"anis% of t"ese reactions( ) &nits lect&re To To ena*le t"e st&dent to +no, and &nderstand t"e f&nda%ental conce#ts of organic c"e%istr! in #re#aration for adanced co&rses in t"e life sciences(
Course Outline I!
STR"CT"RE O# C$R%O& A( HY-RIDI. HY-RIDI.ED ED OR-IT OR-ITALS ALS OF CAR-ON CAR-ON /( Elec Electr tron onic ic con con0g 0g&r &rat atio ion n of car* car*on on 1 ) 1( H!*r H!*rid idi2 i2at atio ion n 3s#$ 3s#$s# s# $s# "!*rid or*itals4 )( 5eo% 5eo%et etr! r! of "!*r "!*rid id or*i or*ita tals ls 6( s and and # c"arac c"aracter ter of "!*r "!*rid id ato%ic ato%ic or*ita or*itals ls -( THE THE CO7 CO7ALEN ALENT T -OND -OND /( C"arac C"aracter terist istics ics of sig% sig%a a and and #i #i or*it or*ital als s 1( For%a or%ati tion on of coa coale lent nt *ond *onds s )( Pro# Pro#er erti ties es of coa coale lent nt *ond *onds s )(/ -ond lengt" )(1 -ond angle )() -ond strengt" )(6 -ond #olarit! )(8 -ond order
II!
C'$SSI#IC$TIO& $&D &OME&C'$T"RE O# ORG$&IC COM(O"&DS A( HYDR HYDROC OCAR AR-ONS ONS /( Unsa Unsat& t&ra rate ted d "!dr "!droc ocar ar*o *ons ns 1( Sat& Sat&ra rate ted d "!d "!drrocar ocar*o *ons ns )( Inde Inde9 9 of "!dr "!drog ogen en de0c de0cie ienc nc! ! -( FUNC FUNCTI TION ONAL AL 5RO 5ROUP UPS S /( 5ro&# I: Halides$ Alco"ols$ Et"ers$ A%ines$ T"iols$ T"ioet"ers 1( 5ro& 5ro&# # II: II: Ald Alde"!d e"!des es$$ ;eton etones es$$ I%i I%ines$ nes$ Acetals$ O9i%es$ H!dra2ones )( 5ro&# III: Nitriles$ Acid Halides$ Car* Car*o9 o9!l !lic ic Acid Acids$ s$ Este Esters rs$$ An An"! "!dr drid ides es$$ A%ides 6( Inde9 of H!drogen De0cienc! 3Halogen$ O9!gen$ and Nitrogen Co%#o&nds4 C( NOMENCLA NOMENCLATURE TURE OF OF OR5ANI OR5ANIC C COMPOU COMPOUNDS NDS
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( Disc&ss Disc&ss t"e t"e ersati ersatilit! lit! of of car*on$ car*on$ %a+in %a+ing g it t"e t"e #rinci#al ele%ent in organic co%#o&nds( 1( Predic edictt t"e t"e t!#e t!#e of "!*r "!*rid idi2 i2at atio ion n of car* car*on on ato%s in a co%#o&nd( )( Dra, Dra, t"e %ole %olec& c&la larr or*i or*ita tall #ict #ict&r &re e of si%# si%#le le organic co%#o&nds( 6( Conert condensed for%&la of organic co%#o&nds co%#o&nds into t"e str&ct&ra str&ct&rall for%&la$ for%&la$ and ice ersa( 8( Pred Predic ictt t"e t"e geo% geo%et etr! r! of orga organi nic c co%# co%#o& o&nd nds s fro% t"e e9#eri%entall! o*sered *ond angles of inorganic co%#o&nds( <( Recogni2e ecogni2e "o, "o, organi organic c co%#o&nds co%#o&nds are are for%ed for%ed *! oerla##ing of ato%ic and "!*rid or*itals( =( Predic Predictt and e9#lai e9#lain n ariatio ariations ns in t"e #ro#ert #ro#erties ies of coa coallent ent *onds onds e9isti istin ng in di>e i>erent ent %olec&lar str&ct&res( At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( Clas Classi siff! orga organi nic c co%# co%#o& o&nd nds s acco accord rdin ing g to co%#osition and f&nctional gro&#s( 1( ?rite rite t"e t"e str& str&ct ct&r &ral al for for%&la %&las s and and gie gie t"e t"e corres#onding IUPAC and@or co%%on na%e of organic co%#o&nds( )( Dete Deter% r%in ine e t"e t"e inde inde9 9 of "!dr "!drog ogen en de0c de0cie ienc nc! ! for eac" for%&la and ,rite *ot" t"e c!clic and ac!clic str&ct&re to 0t eac" for%&la( 6( Identi Identif! f! t"e f&nct f&nction ional al gro&# gro&# of eac" eac" class class of organic co%#o&nd( 8( 5ie ie e9a%# 9a%#le les s of *iol *iolog ogic ical al i%#o i%#ort rtan ance ce of eac" class of organic co%#o&nds(
)(
III!
STR"CT"RE O# ORG$&IC COM(O"&DS A( ISOMERISM /( Str&ct&ral iso%ers 3c"ain$ f&nctional$ #ositional4 1( Stereoiso%ers 1(/ Confor%ational iso%ers 1(1 Confor%ational anal!sis 1() 5eo%etric iso%ers 1(6 E$. no%enclat&re of geo%etric iso%ers 1(8 O#tical iso%ers 1(< R$S no%enclat&re of o#tical iso%ers #IRST DE($RTME&T$' E)$MI&$TIO&
I*!
STR"CT"R$' E##ECTS O& (HYSIC$' $&D CHEMIC$' (RO(ERTIES A( STRUCTURAL EFFECTS /( Resonance 3#i electron delocali2ation4 1( CH "!#erconB&gation )( 7an der ?aals interaction 6( H!drogen *onding 8( Steric e>ects <( Ind&ctie e>ects -( -OILIN5 POINT AND MELTIN5 POINT /( Inter%olec&lar attractions: London forces$ di#oledi#ole interactions "!drogen *onding 1( E>ect of car*on c"ain lengt" )( E>ect of car*on *ranc"ing 6( E>ect of %olec&lar s!%%etr! 3cis trans for geo%etric iso%ers ort"o#ara for aro%atic co%#o&nds4 8( E>ect of #olarit! <( E>ect of f&nctional gro&#s t"at are ca#a*le of H*onding interactions 3inter%olec&lar and intra%olec&lar H *onding4 C( SOLU-ILITY /( Polar and non#olar solents 1( Protic and a#rotic #olar solents )( H!dro#"ilic and "!dro#"o*ic co%#o&nds 6( E>ect of car*on c"ain lengt" 8( E>ect of #olar f&nctional gro&#s D( ACIDITY AND -ASICITY /( #;a and #;* of #arent car*on acids$ nitrogen acids$ and o9!gen acids 1( Strengt" of conB&gate *ase )( Str&ct&ral e>ects on acidit! and *asicit! E( AROMATICITY /( Str&ct&ral #ro#erties of co%#o&nds t"at e9"i*it aro%aticit! 1( H&c+el r&le
Sta*ilit! of aro%atic co%#o&nds
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( Di>erentiate *et,een str&ct&ral iso%ers and stereoiso%ers( 1( Di>erentiate *et,een con0g&rational iso%ers and confor%ational iso%ers( )( Anal!2e t"e di>erent t!#es of confor%ations( 6( Identif! t"e factors &sed to #redict t"e sta*ilit! of confor%ations( 8( Identif! t"e di>erent +inds of con0g&rational iso%ers and t"eir #ro#erties( #IRST DE($RTME&T$' E)$MI&$TIO& At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( De0ne and correlate t"e ario&s str&ct&ral e>ects ,it" t"e di>erent #ro#erties of organic co%#o&nds( 1( Descri*e t"e di>erent inter%olec&lar forces of attraction( )( Co%#are t"e *oiling #oints and %elting #oints of *ranc"ed and linear "!drocar*ons o#en and c!clic "!drocar*ons and "!drocar*on deriaties( 6( Di>erentiate *et,een #olar and non#olar solents #rotic and a#rotic solents "!dro#"o*ic and "!dro#"ilic co%#o&nds( 8( Predict t"e sol&*ilit! of a #artic&lar organic co%#o&nd in #olar and non#olar solents #rotic and a#rotic solents( <( E9#lain t"e acidit! and *asicit! of a #artic&lar organic co%#o&nd *ased on resonance and ind&ctie e>ects( =( Co%#are t"e acidit! of organic co%#o&nds ,"en dissoled in t,o +inds of solents( ( Identif! aro%atic co%#o&nds(
*! I&TROD"CTIO& TO ORG$&IC RE$CTIO&S $! CHARACTERISTIC REACTION OF OR5ANIC COMPOUNDS /( Acid*ase reaction 1( Reactions t"at %a+e or *rea+ *onds 1(/ Addition 1(1 S&*stit&tion 1() Eli%ination 1(6 Rearrange%ent )( Redo9 reaction -( TYPES OF -OND CLEA7A5E: HOMOLYTIC AND HETEROLYTIC -REA;IN5 C( TYPES OF REACTION INTERMEDIATES AND MECHANISM /( Concerted and %<iste# #rocesses 1( Sta*ilit! of inter%ediates D( MAOR CLASSES OF REACTI7E PARTICLES /( Electro#"iles and n&cleo#"iles 1( Strengt" of n&cleo#"iles
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( En&%erate t"e general c"aracteristic reactions of organic co%#o&nds( 1( Predict t"e t!#e of reaction 3s&*stit&tion$ eli%ination$ redo9$ rearrange%ent4 )( Identif! t"e t!#e of *ond *rea+ing 3"o%ol!tic or "eterol!tic *rea+ing4 6( Eal&ate t"e sta*ilit! of t"e di>erent +inds of reaction inter%ediates( 8( Di>erentiate concerted and %<itste# reaction #rocesses( <( Di>erentiate *et,een electro#"iles and n&cleo#"iles( =( Di>erentiate *et,een n&cleo#"ilicit! and *asicit!( ( Eal&ate t"e strengt" of n&cleo#"iles( ( Deter%ine t"e o9idation n&%*er of car*on in organic co%#o&nds(
SECO&D DE($RTME&T$' E)$MI&$TIO& SECO&D DE($RTME&T$' E)$MI&$TIO& *I!
RE$CTIO&S RE$GE&TS
I&*O'*I&G
E'ECTRO(HI'IC
A( FREE RADICAL SU-STITUTION AT SATURATED CAR-ON /( Free radical %ec"anis% of "alogenations 1( Relatie reactiit! of "alogens to free radical s&*stit&tion reaction )( Relatie reactiit! of al+anes to "alogenation reaction
-( ELECTROPHILIC ADDITION /( 5eneral reaction %ec"anis% of electro#"ilic addition reaction 1( Direction and stereoc"e%istr! of added s&*stit&ent )( Orientation and #osition o f added s&*stit&ent 6( Relatie rates of car*oni&% ion inter%ediates 8( Addition reactions of al+enes <( Addition reactions of al+!nes =( Mec"anis% of conB&gate addition reaction ( /$1 and /$6addition reactions of *&tadiene
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( S"o, t"e %ec"anis% of free radical s&*stit&tion reaction( 1( De0ne t"e condition t"at ,ill li%it s&*stit&tion to %ono"alogenation( )( Predict t"e n&%*er of %ono"alogenation #rod&cts #ossi*le for a gien al+ane( 6( Eal&ate t"e reactiit! of "alogenation reaction 3c"lorination s *ro%ination4 8( Deter%ine t"e #ercentage !ield of %ono"alogenated #rod&cts(
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( S"o, t"e %ec"anis% of electro#"ilic addition reaction( 1( Predict t"e orientation and #osition of added s&*stit&ent to al+enes( )( Co%#are t"e sta*ilit! of t"e reactie inter%ediates( 6( Co%#are electro#"ilic addition reactions of al+enes and al+!nes( 8( S"o, t"e %ec"anis% of conB&gate addition reaction(
<( Deter%ine t"e %aBor #rod&ct of conB&gate addition reaction(
C(
ELECTROPHILIC AROMATIC SU-STITUTION /( T"e *en2ene ring: geo%etr! and #i electrons 1( Mec"anis% of electro#"ilic aro%atic s&*stit&tion 1(/ 5eneration of electro#"iles 1(1 Attac+ of electro#"iles on t"e aro%atic ring 1() Resonance str&ct&re of *en2eneoni&% ion 1(6 Ne&trali2ation of *en2eneoni&% and generation of catal!sts )( E>ect of s&*stit&ent gro&#s on reactiit! and orientation 6( Classi0cation of s&*stit&ents: ort"o$ #ara$ %eta directors actiating$ deactiating gro&#s 8( Molec&lar *asis of reactiit! and orientation 8(/ Electron release ia resonance 8(1 Ind&ctie e>ect 8() E>ect of "alogens: deactiating$ ort"o#ara directors <( Reactiit! of dis&*stit&ted *en2ene =( Li%itation of FriedelCrafts al+!lation@ac!lation reaction ( O9idation of al+!l*en2ene and red&ction of aceto#"enone ( S!nt"esis of organic co%#o&nds
*II!
RE$CTIO&S RE$GE&TS
I&*O'*I&G
&"C'EO(HI'IC
A( NUCLEOPHILIC AROMATIC SU-STITUTION /( Reactiit! to,ards n&cleo#"ilic aro%atic s&*stit&tion 1( Introd&ction of n&cleo#"iles to *en2ene ring t"ro&g" dia2oti2ation )( Mec"anis% of dia2oti2ation for #ri%ar! and secondar! a%ines 6( Sta*ilit! of aro%atic dia2oni&% ion 8( Organic s!nt"esis of d!e
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( S"o, t"e %ec"anis% of electro#"ilic aro%atic s&*stit&tion( 1( Identif! ort"o#ara and %eta directors( )( E9#lain t"e e>ect of s&*stit&ents on t"e reactiit! of aro%atic co%#o&nds( 6( Predict t"e reactiit! of %onos&*stit&ted and dis&*stit&ted *en2ene to,ards electro#"ilic aro%atic s&*stit&tion( 8( Predict t"e orientation of inco%ing s&*stit&ent in %ono and dis&*stit&ted *en2ene( <( E9#lain ,"! "alogen ato%s are ort"o#ara directors( =( ;no, t"e li%itations of FriedelCrafts al+!lation and ac!lation reactions( ( S!nt"esi2e aro%atic co%#o&nds(
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( Identif! t"e conditions necessar! for a co%#o&nd to &ndergo n&cleo#"ilic aro%atic s&*stit&tion( 1( S"o, t"e %ec"anis% for t"e for%ation of dia2oni&% salt( )( ?rite so%e n&cleo#"ilic s&*stit&tion reactions of dia2oni&% salts(
THIRD DE($RTME&T$' E)$MI&$TIO& THIRD DE($RTME&T$' E)$MI&$TIO&
6(1 6() -( NUCLEOPHILIC SU-STITUTION AT SATURATED CAR-ON /( Mec"anis% of SN/ and SN1 reactions 1( Stereoc"e%istr! of SN/@SN1 )( Rate of SN/@SN1 reactions 6( Factors a>ecting rate of SN/@SN1 reactions 6(/ Nat&re of s&*strate 6(1 Strengt" of n&cleo#"iles 6() Nat&re of leaing gro&# 6(6 E>ect of solent 8( Co%#eting reactions: e li%ination$ rearrange%ent <( S&*stit&tion reactions of alco"ols and et"ers =( Intra%olec&lar s&*stit&tion reactions
C( ELIMINATION /( Mec"anis% of E/@E1 reactions 1( Conditions fao&ring eli%ination reactions: strong *ases$ "ig"er te%#erat&re )( Reactiit! of s&*strates to,ards eli%ination reactions 6( Sta*ilit! of al+enes 8( Ho>%ann eli%ination reaction
D( NUCLEOPHILIC ADDITION TO UNSATURATED CAR-ON 3CAR-ONYL AND RELATED 5ROUPS4 /( Mec"anis% of acidcatal!sed and *asecatal!sed reaction 1( Factors a>ecting reactiit! of car*on gro&#s 1(/ Resonance 1(1 Ind&ctie e>ect 1() Steric e>ect )( Si%#le addition reaction )(/ Addition of HCN )(1 Addition of NaHSO) )() Halofor% reaction )(6 Addition of 5rignard Reagent )(8 Addition reaction of conB&gated alde"!des@+etones )(< Mec"anis% of aldol condensation and Canni22aro reaction 6( Addition follo,ed *! eli%ination 6(/ Condensation reaction ,it" nitrogen co%#o&nds
Acetal and "e%iacetal for%ation Strec+er s!nt"esis of a%ino acids
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( Co%#are t"e reactiit! of al+!l "alides to,ards SN/ and SN1 reactions( 1( S"o, t"e %ec"anis% of SN/ and SN1 reactions( )( Identif! t"e conditions t"at fao&r SN/ and SN1( 6( Di>erentiate stereoc"e%istr! of SN/ and SN1 reactions( 8( Predict ,"en eli%ination can co%#ete ,it" s&*stit&tion( <( S"o, t"e %ec"anis% of s&*stit&tion reaction of alco"ols 3SN/ and SN14( =( S"o, t"e %ec"anis% of s&*stit&tion reaction of et"ers( ( S"o, t"e %ec"anis% of intra%olec&lar s&*stit&tion reactions( At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( S"o, E/ and E1 %ec"anis%s( 1( Identif! t"e conditions fao&ring eli%ination reactions( )( Co%#are t"e reactiit! of al+!l "alides and alco"ols to,ards eli%ination reactions( 6( Co%#are t"e %ec"anis%s of de"!dration of alco"ols and de"!dration of al+!l "alides( 8( Predict t"e %aBor #rod&ct *ased on t"e .aitse r&le( <( ;no, t"e conditions t"at fao&r Hof%ann eli%ination reactions( At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( Ill&strate t"e acid and *ase catal!2ed addition reaction %ec"anis%s of alde"!des and +etones( 1( Recogni2e t"e factors a>ecting t"e reactiit! of car*on!l gro&#s( )( Co%#are t"e reactiit! of so%e car*on containing co%#o&nds( 6( Predict t"e %ec"anis% of addition of HCN and NaHSO ) to alde"!des and +etones( 8( S"o, t"e %ec"anis% of t"e follo,ing reactions: "alofor% reaction$ aldol condensation$ acetal and "e%iacetal for%ation$ condensation reaction of nitrogen co%#o&nds$ and 5rignard reaction( <( Identif! t"e n&cleo#"iles t"at ,ill faor conB&gate addition and direct addition to conB&gated alde"!des and +etones(
=( S"o, t"e %ec"anis% of Strec+er s!nt"esis of a%ino acids(
E( NUCLEOPHILIC SU-STITUTION AT UNSATURATED CAR-ON /( Mec"anis% of n&cleo#"ilic s&*stit&tion 1( Reactiit! of leaing gro&#s in car*o9!lic acid deriaties 1(/ -asicit! of leaing gro&#s 1(1 Resonance of s&*stances 1() Co%#aratie reaction of *ases or n&cleo#"iles to sat&rated and &nsat&rated car*on )( Reactions of car*o9!lic acid deriaties )(/ Esteri0cation and transesteri0cation )(1 -ase "!drol!sis of esters: sa#oni0cation )() S!nt"esis of an"!drides )(6 S!nt"esis of as#irin and oil of ,intergreen *III! REDO) RE$CTIO&S A( COMMON OGIDI.IN5 AND REDUCIN5 A5ENTS -( SOME USES OF REDOG REACTIONS /( In '&alitatie anal!sis /(/ -ae!ers Test /(1 Tollens Test /() Fe"lings Test /(6 -enedicts Test 1 In organic s!nt"esis 1(/ O9idation ,it" ;MnO6$ ; 1Cr1O= 1(1 Red&ction 1(1(/ Catal!tic H!drogenation 1(1(1 Cle%%ensen Red&ction 1(1() Red&ction ,it" LiAlH 6@Na-H6 1(1(6 Red&ction ,it" Metal 3Sn4 )( In str&ct&re deter%ination: o2onol!sis )(/ Red&ctie o2onol!sis )(1 O9idatie o2onol!sis #O"RTH DE($RTME&T$' E)$MI&$TIO&
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: 1! Recogni2e car*o9!lic acids and t"eir deriaties( +! E9#lain t"e reactiit! of car*o9!lic acids and t"eir deriaties( 3! Co%#are t"e reactiit! of *ase@n&cleo#"iles to co%#o&nds containing sat&rated and &nsat&rated car*on 3e(g( ac!l c"lorides and al+!l c"lorides$ a%ides and a%ines4(
At t"e end of t"e &nit$ t"e st&dents s"o&ld *e a*le to: /( Identif! so%e o9idi2ing and red&cing agents( 1( Cite so%e redo9 reactions in: a( &alitatie anal!sis of so%e organic co%#o&nds *( Organic s!nt"esis c( Str&ct&re deter%ination of al+enes
#O"RTH DE($RTME&T$' E)$MI&$TIO&
Course (olicies: /( An! for% of c"eating d&ring e9a%inations s"all *e #enali2ed according to t"e f&llest e9tent of &niersit! r&les and reg&lations( T"e case against o>enders s"all *e 0led and referred to t"e "ig"est a&t"orities regarding sc"olastic integrit! and t"eir f&t&re in t"e &niersit!( F&rt"er%ore$ a grade of 8(J is a&to%aticall! gien to t"e o>enders and t"e! s"all *e *lac+listed as c"eaters in t"eir s&cceeding se%esters ta+ing an! c"e%istr! s&*Bect in t"e diision( 1( No %a+e&# e9a%ination s"all *e gien for ,"ateer reason( )( In case an e9a%ination is %issed d&e to a alid reason$ t"e 0nal e9a%ination s"all %a+e &# for t"e %issed e9a%ination( No %ore t"an t,o %issed e9a%inations s"all *e allo,ed( 6( A st&dent is e9e%#ted fro% ta+ing t"e 0nal e9a%ination if t"e follo,ing conditions are %et: a( He@s"e "as a class standing e'&ialent to a grade of 1(=8 or *etter( *( He@s"e "as no grade lo,er t"an 6JK in an! of t"e long e9a%inations( 8( At t"e end of t"e se%ester$ grades s"all *e co%#&ted as follo,s: a( If t"e st&dent ta+es t"e 0nal e9a%ination$ "is or "er grade s"all *e co%#&ted according to t"e follo,ing #ercentage distri*&tion: Class Standing: 1@) Final E9a%ination: /@) *( If a st&dent is e9e%#ted fro% ta+ing t"e 0nal e9a%ination and did not ta+e it$ t"en "is or "er grade s"all *e t"e e'&ialent grade of "is or "er class standing( c( If a st&dent is not e9e%#ted *&t failed to ta+e t"e 0nal e9a%ination for ,"ateer reason$ "e or s"e gets a grade of 8(J(
Course Re,uire-ents: • • •
Fo&r 364 De#art%ental E9a%inations &i22es PreFinal 5rade
PreFinal 5rade Final E9a%ination Final 5rade
1@) /@) /
Gradin. Scale: J/JJ 8 J6 =8= =J=6
/(JJ /(18 /(8J /(=8 1(JJ
JK 1JK /JJK
<8<
C/ristop/er 0a T! Robidillo2 MS Su--er2 $Y +114+1+
prepared_by_threelegendz_summer_11_12
1(18 1(8J 1(=8 )(JJ 6(JJ 8(JJ
