Organic Chemistry (CHE 24) Laboratory Manual

Department of Chemistry Centre College

Fall !!" #ennifer Mu$y%a #oe &or%man

'able of Contents
Laboratory Schedule........................................................................................................................3 Safety in the Laboratory...................................................................................................................4 Introduction to the Laboratory.........................................................................................................6 Glassware used in Organic Lab.......................................................................................................8 Recrystallization of an n!nown Solid .........................................................................................." #he Iso$ers of %6&'4( )ractional *istillation and +,R S-ectrosco-y ....................................'' .cid/0ase 12traction.....................................................................................................................'3 %hro$atogra-hy ...........................................................................................................................'8 %he$ical Shift and Integration in the +,R .................................................................................'" S-in/S-in S-litting in '& +,R S-ectrosco-y ............................................................................44 %affeine .........................................................................................................................................44 Orientation to S-artan....................................................................................................................46 S-artan 12ercise. Rotational 0arriers in .l!anes ........................................................................35 %onfor$ations of ,olecules .........................................................................................................3' %o$-etiti6e +ucleo-hiles 7ith '/0utanol....................................................................................33 *ehydration of %yclohe2anol........................................................................................................38 Identification of an n!nown .......................................................................................................3" .--endi2........................................................................................................................................44

Laboratory (che)ule
Date Se-t. 89 '5 Se-t. '39 '8 Se-t. 449 44 Se-t. 4"9 Oct. ' Oct. 69 8 Oct. 459 44 Oct. 489 4" +o6. 39 3 +o6. '59 '4 +o6. '89 '" E*periment Recrystallization of an n!nown Solid #he Iso$ers of %6&'4( )ractional *istillation and +,R S-ectrosco-y .cid/0ase 12traction %hro$atogra-hy an) %he$ical Shift and Integration in the +,R S-in/S-in S-litting in '& +,R S-ectrosco-y %affeine %onfor$ations of ,olecules %o$-etiti6e +ucleo-hiles 7ith '/0utanol *ehydration of %yclohe2anol Identification of an n!nown

(afety in the Laboratory

#he best rule for laboratory safety is to thin!9 and to thin! ahead. 7hen you are ade:uately -re-ared you will wor! safely and $ore efficiently and -rofit $ore for your ti$e in6ested. #he che$istry laboratory is a dangerous -lace but -robably no $ore so than the ho$e !itchen or wor!sho-. .ccidents ha--en -ri$arily when -eo-le use the wrong techni:ues9 don;t !now what they are doing9 or rush. <lease read the following safety rules carefully and follow the$ whene6er you wor! in the laboratory. ,any of the substances encountered in the organic lab are to2ic9 fla$$able9 or both. &owe6er9 e2-osure has been $ini$ized due to the s$all scale at which we wor!. .lso9 $ost o-erations in6ol6ing heating che$icals are done without fla$es. It is still i$-ortant to use correct techni:ues in handling che$icals and to !now the hazards that are -resent. 16ery student is res-onsible for !nowing and following the safety guidelines outlined by the instructor on the first day. +mportant( Safety goggles $ust be worn in the lab at all ti$es. #hese $ust be -ro6ided by the student and are a6ailable for -urchase in the %entre Sho--es. #he instructor $ust a--ro6e goggles -urchased elsewhere. .ll students $ust wear long -ants or s!irts and shoes with co6ered toes =no shorts or sandals> in the lab. Failure to follo, the safety proce)ures ,ill result in )ismissal from the class ,ith a gra)e of -. ='> =4> Safety glasses $ust be worn at all ti$es in the laboratory. #his regulation is treated 6ery conscientiously. *uring the first laboratory -eriod fa$iliarize yourself with the location and o-eration of all safety e:ui-$ent in the laboratory. #hese features include the safety shower9 fire e2tinguisher9 laboratory first aid !its9 eye wash station9 and fire alar$. <lease fa$iliarize yourself with the alternate e2its fro$ the lab. #he safety shower should be used if your clothing catches on fire or if a corrosi6e che$ical is s-illed on you in :uantities that cannot be easily flushed away at the laboratory faucets. %uts and burns are the $ost co$$on in?uries occurring in che$istry laboratories. #he best i$$ediate first aid for such accidents is to flush with co-ious a$ounts of water to assure that any che$icals are washed out of a cut or off of irritated s!in. %onsult the laboratory instructor about further first aid $easures. If you co$e to the laboratory with a cut or burn9 it is i$-ortant that the wound be -rotected by an a--ro-riate bandage. ,ost laboratory che$icals used in this course are to2ic9 -articularly in the concentrations handled. #he e2ce-tions to this are so few as to $a!e any tasting utterly foolish. Regulatory action by the Occu-ational Safety and &ealth .d$inistration re:uires all che$ical su--liers to -ro6ide9 for all of their -roducts9 co-ies of ,aterial Safety *ata Sheets =,S*S>. #hese docu$ents describe the a--ro-riate handling -recautions9 dis-osal -rocedures9 and first aid ste-s for each substance. #he %he$istry -rogra$ !ee-s a file of all of these ,S*S docu$ents in the stoc!roo$. @ou should consult that file if you are uncertain about the -ro-erties of any che$ical. %lothing. Shoes $ust be worn at all ti$es. #here is often bro!en glass or s-illed che$icals on the laboratory floor. Loose fitting clothes9 es-ecially long slee6es and nec!ties9 are a definite safety hazard. #hey can easily fall into bea!ers or !noc! o6er a hazardous che$ical.

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3 =8> =8> ="> ='5> =''> ='4> ='3> ='4> Long hair9 if left hanging loosely9 can be a real hazard. <lease !ee- long hair Atied bac!A in so$e fashion. Bewelry can also catch on -rotruding ob?ects and lead to accidents. Bust dro- your watch9 rings9 bracelets9 and nec!laces into a free -oc!et when you co$e to lab. +e6er -lace coats9 boo!s9 or other belongings on the bench or floor where they will interfere with your wor!9 be da$aged by reagent s-ills9 or -ose a safety -roble$. .ny e2-eri$ent in6ol6ing the use of9 or -roduction of9 -oisonous or irritating gases $ust be -erfor$ed in the hoods. )ood and be6erages are not allowed in the laboratory. se of all tobacco -roducts in the lab is li!ewise not allowed. &orse-lay and unauthorized e2-eri$ents are strictly forbidden. +e6er use $outh suction to -i-et li:uids. Instead9 use a -i-et bulb to a--ly suction. Read the label carefully before ta!ing anything fro$ a bottle. ,any che$icals ha6e si$ilar na$es9 such as sodiu$ sulfate and sodiu$ sulfiteC it is ob6ious that the use of the wrong reagent can s-oil an e2-eri$ent or9 in so$e cases9 cause a serious accident. *o not carry reagent bottles to your wor! s-ace. #his is a $atter of courtesy to the other students in the class9 and it $ini$izes the -ossibility of conta$ination of the reagent. Obtain the re:uired :uantities of che$icals fro$ the reagent shelf by ta!ing clean test tubes or bea!ers to the reagent area. *o not insert s-atulas or $edicine dro--ers into reagent bottles. Re$o6e a li:uid reagent fro$ the stoc! container by -ouring it into a clean bea!er. Solid reagents $ay be transferred by gentle rotation of the container. +e6er return e2cess reagent to the original container. It is true that high -urity che$icals are e2-ensi6e9 but the hazards in6ol6ed and the -ossibility of ruined e2-eri$ents due to conta$inated su--lies are a greater consideration than the costs in6ol6ed. *is-ose of all trash and che$icals -ro-erly. =a> Ordinary trash cans are -ro6ided for -a-er. =b> S-ecial rece-tacles =often a cardboard bo2 labeled Glass> are -ro6ided for dis-osal of bro!en glass. =c> Low to2icity water soluble li:uids =alcohols9 acetone9 dilute acids9 etc.> and low to2icity water/soluble solids are best dis-osed of by flushing down the sin! with large 6olu$es of water. =d> S-ecially $ar!ed dis-osal cans are a6ailable for water i$$iscible li:uids. =e> 7hene6er strong o2idizing agents9 -articularly to2ic substances or $aterials re:uiring s-ecial handling are used in the lab9 detailed instructions will be gi6en and a--ro-riate dis-osal facilities will be -ro6ided. Re-ort all accidents and s-ills to the laboratory instructor i$$ediately.

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+ntro)uction to the Laboratory

Laboratory is an integral -art of your organic che$istry course. In the laboratory you will obser6e so$e of the -ro-erties described in class. @ou will also learn the basic techni:ues of wor!ing with organic co$-ounds that are e$-loyed by organic che$ists. #he e$-hasis in lab will be on understanding results rather than obtaining -roducts. #en -ercent of your o6erall grade will be based on lab( attendance9 noteboo! =yellow -ages>9 short re-orts9 :uizzes9 and techni:ue. In addition9 a--ro2i$ately '5D of each e2a$ will be based on $aterial fro$ the laboratory. (che)ule. Laboratory $eets wee!ly on #uesdays and #hursdays. ,ost of the $eetings begin with a briefing session. 16ery student is e2-ected to be -resent and wor!ing during the assigned -eriod. If additional ti$e is needed to co$-lete labs9 students $ust obtain -er$ission fro$ the instructor to wor! in the lab. nsu-er6ised wor! on wee!ends or in the e6ening is -rohibited. E*periments. 1ach student is e2-ected to -re-are before co$ing to lab by reading the assigned bac!ground infor$ation. Students are e2-ected to wor! indi6idually unless directed otherwise. Laboratory E/uipment. .ll students will share a large -ool of $icroscale glassware. It is essential that all glassware be cleaned and dried -rior to lea6ing the lab. In addition9 the lab wor!s-ace $ust also be cleaned. Students will alternate cleaning the balance area and the s$all roo$ ne2t to the lab. )ailure to follow these -rocedures will result in -oints being deducted fro$ the final grade. Laboratory Data an) 0eports. 1ach student $ust ha6e a noteboo! for !ee-ing laboratory obser6ations and data in )uplicate. #he <relab and Lab wor! sections described below should be written in your lab noteboo!. #he yellow carbon co-ies will be turned in for grading. <relab =#his section should be co$-leted before you start the e2-eri$ent.> ='> +ntro)uction. 7rite a brief sentence or two describing what you e2-ect to learn or acco$-lish. Gi6e a literature reference for the -rocedure. =7here did you get the -rocedure to followE Gi6e -age nu$ber and authorsF> =4> 0eaction summary. #his section includes a balanced e:uation and a $echanis$ for each che$ical reaction that too! -lace. =3> 'able of 0eagents an) 1ro)ucts. Include co$-ound na$e9 $olecular weight9 structure9 a$ount used =in gra$s or $L and MOLES>9 and -ertinent data =i.e.9 $elting -oint9 solubility9 density9 concentration>. Lab 7or! =4> Data an) Obser2ations. #his section of the lab noteboo! contains what you did and what you saw. Do not simply copy the experimental procedure from the lab manualC that will be a certain $ethod for losing -oints on the lab. 0e sure to re-ort the e2act a$ount of che$icals used. #he balances in the lab gi6e $ore than one deci$al -laceC re-ort all the deci$al -laces. So$eti$es it will be easier to weigh li:uids than to $easure the$ by 6olu$e. Obser6ations include such things as color9 s$ell =be careful here>9 6iscosity9 and -hysical state =solid or li:uid>. 0e sure to !ee- trac! of the reaction ti$es for each ste-

8 carried out. 3l,ays $easure the $ass of the final -roduct you isolate. State how the -roduct was characterized. ,easured -hysical -ro-erties should be included in your noteboo! when these obser6ations are obtained. Results and %onclusions =3> 4iel) )ata. =a> %ite e6idence that your -roduct is the correct one. %o$-are -hysical data to literature 6alues =$-9 b-9 s-ectrosco-ic data9 etc.>. 1sti$ate -roduct -urity. =b> Include all nu$erical data =units labeled>9 well/labeled calculations =especially percent yield>9 and gra-hs. .nalyze the data. =5ote( @ou $ay need to refer to your general che$istry te2tboo! to re6iew calculations for -ercent reco6ery and -ercent yield.> =6> Conclusions. 12-lain what i$-urity is re$o6ed in each -urification ste-. *iscuss any errors that $ay ha6e caused your results to de6iate fro$ what was e2-ected. Su$$arize what you learned. Include answers to :uestions assigned by your instructor in the te2t of your conclusions. *iscuss $ore than ?ust loss due to the -hysical li$itations of the e:ui-$ent. )or instance9 if you ha6e less than a '55D yield there are $ore reasons than ?ust ASo$e of the solid stuc! to the flas! and so$e -assed through the filter -a-er.A

#echni:ue includes -re-aredness =-ossible :uizzes>9 -roduct yield9 and -roduct -urity. @ou will lose -oints for yield and -urity only in unusual circu$stancesC it is not worth your ti$e to s-end fore6er in lab trying to get e6ery detail -erfectly correct. #here are a few -oints you $ust !ee- in $ind for all of the e2-eri$ents. ='> Gee- a little of each inter$ediate for analysis. =4> *o not discard any inter$ediates or -roductsC 6ials will be set u- for their collection. =3> Gee- an accurate record of all lab wor! in your noteboo!. =4> 0e careful about -ouring che$icals down the sin!C when in doubt9 .SGF =3> *o not store -roducts in conical 6ialsC use storage 6ials or -etri dishes instead. =6> *o not lea6e ther$o$eters in the alu$inu$ bloc!s. 7e will not $onitor te$-erature this way9 and itHs an easy way to brea! the ther$o$eters. =8> *o not turn the hot-lates -ast 3 unless the instructor tells you otherwise.

6lass,are use) in Organic Lab

6acuu$ round botto$ flas!

ada-ter

%laisen head

still head

centrifuge tube

filter flas! se-aratory funnel

condenser

drying tube

s-in 6ane

&ic!$an still head

conical 6ial

&irsch funnel

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0ecrystalli$ation of an -n%no,n (oli)

7ac%groun) %rystalline co$-ounds are generally -urified 6ia recrystallization. In a recrystallization9 we dissol6e the i$-ure solid in a $ini$u$ a$ount of hot sol6ent and then allow crystals to for$ slowly. It is i$-ortant to choose a sol6ent which will not dissol6e the substance at roo$ te$-erature so that the -ure crystals $ay be reco6ered. If too $uch sol6ent is used9 the reco6ery of sa$-le will be decreased. If the sol6ent is not hot when the dissolution is carried out9 too $uch sol6ent will be used9 leading to di$inished yield. #his -urification $ethod ta!es ad6antage of the differences in solubility between the co$-ound and its i$-urities. ,ost of the i$-urities will re$ain dissol6ed in the cool sol6ent9 allowing the$ to be re$o6ed when the sa$-le is isolated by 6acuu$ filtration. So$e of the i$-urities $ay not dissol6e e6en in hot sol6ent9 re:uiring a hot filtration to re$o6e the$. Occasionally the crystals $ay not for$ as the solution cools. #here are a few ste-s that can be ta!en to induce crystallization in these cases. #hese include( =a> using a seed crystal9 =b> scratching the inside of the flas!9 =c> cooling the $i2ture in an ice bath9 and =d> re$o6ing so$e of the e2cess sol6ent by boiling9 then allowing the $i2ture to cool again. Seed crystals and flas! scratching both induce crystallization by -ro6iding a surface on which the crystals can begin for$ing. It is i$-ortant to al,ays sa6e so$e i$-ure sa$-le to use as seed crystals. Once the crystals ha6e for$ed9 the sa$-le should be cooled in an ice bath to $a2i$ize the reco6ery. #he crystals are then isolated using 6acuu$ filtration. In organic lab9 these 6acuu$ filtrations are ty-ically carried out using a &irsch funnel and a filter flas!9 as shown below. @ou should always use a clean filter flas! =instead of using one left behind by a class$ate>9 in case you need to re/filter the sa$-le or ta!e a second cro- of crystals. )inally9 you should wash your crystals with a small a$ount of col) sol6ent to wash away any i$-urities. 0efore you obtain a $elting -oint or weight of your sa$-le9 be sure that the sa$-le has dried ade:uately. Re$aining sol6ent will gi6e erroneously high weights9 and it is an i$-urity that will influence the -hysical -ro-erties of your -roduct.

)igure9 &irsch funnel with )ilter flas!9 used to isolate recrystallized sa$-le.

'5 Melting points @ou should re$e$ber the discussion of colligati6e -ro-erties fro$ %&1 43. =If not9 reread that cha-ter in your general che$istry te2tboo!.> %olligati6e -ro-erties9 li!e boiling -oint ele6ation and $elting -oint de-ression9 de-end on the nu$ber of solute -articles in a sol6ent. sing salt to $elt ice on the roads is an e2a$-le of a colligati6e -ro-erty. Bust as salt lowers the $elting -oint of the ice9 i$-urities lower the $elting -oints of organic co$-ounds. #hus9 the -urity of a co$-ound $ay be /ualitati2ely assessed by ta!ing its $elting -oint. In addition to lowering the $elting -oint9 i$-urities also widen the $elting -oint range. @ou should al,ays re-ort the entire $elting range of a sa$-le for that reason. Li!ewise9 it is good -ractice to co$-are your e2-eri$entally deter$ined $elting -oint with the literature $elting -oint of the -ure co$-ound. Procedure &eat a bea!er of water to a gentle boil on a hot -late to use as a heating $ediu$. @ou will first need to deter$ine the solubility of your un!nown in se6eral co$$on sol6ents =water9 ethanol9 -etroleu$ ether9 dichloro$ethane9 ethyl acetate>. <lace about 45 $g =a s$all s-atula/tifull> of finely crushed un!nown in each of se6eral test tubes and add about 5.3 $L of each sol6ent to the different tubes containing the solid. Stir each $i2ture and deter$ine whether the solid is soluble in each sol6ent at roo$ te$-erature. If the un!nown is not soluble in a gi6en sol6ent9 -lace the test tube in the hot water bath. Stir or swirl the tube9 obser6ing whether the solid is soluble in hot sol6ent. .llow the hot solutions to cool slowly to roo$ te$-erature. If crystals for$ in the cooled $i2tures9 co$-are their :uantity9 size9 color9 and for$ with the original solid $aterial. It $ay be hel-ful to construct a table containing the solubility data9 fro$ which you should be able to decide the sol6ent that a--ears best suited for recrystallization. Once you ha6e deter$ined which sol6ent will be $ost effecti6e for recrystallizing your un!nown sa$-le9 dissol6e your sa$-le in a $ini$u$ a$ount of hot sol6ent. Sa6e a s-atulaful of your i$-ure sa$-le for seed crystals and to co$-are its $elting -oint to your recrystallized sa$-le. sing an 1rlen$eyer flas!9 add the hot sol6ent to the solid. *o +O# add the solid to the hot sol6ent. &ot filter the sa$-le if necessary. .llow the solution to cool slowly to allow crystals to for$. Once the sa$-le has cooled to roo$ te$-erature9 -lace it in an ice bath to co$-lete the crystallization. If necessary9 you $ay induce crystallization by scratching the inside of the flas! with a stirring rod =rough end>9 cooling your sa$-le in an ice bath9 or adding a seed crystal. If your sa$-le oils out9 heat it u- again and add $ore sol6ent before allowing it to cool again. %ollect the crystals by 6acuu$ filtration using a &irsch funnel. 7ash the crystals with a s$all -ortion of cold sol6ent. .llow the crystals to air dry o6ernight before deter$ining the weight and $elting -oint of your -urified sa$-le. )or your lab re-ort9 calculate the -ercent reco6ery of the -ure crystals that you obtain. %o$$ent on the -urity of your crystals and on the -ercent reco6ery.

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'he +somers of C8H 49 Fractional Distillation an) 5M0 (pectroscopy

)igure '9 Si$-le *istillation .--aratus Distillation Li:uids are usually -urified by distillation. Si$-le distillation =)igure '> will allow you to re$o6e non/6olatile i$-urities =with 6ery high boiling -oints> fro$ a li:uid. Si$-le distillation wor!s well for se-arating sodiu$ chloride =b- '4'3 o%> fro$ water =b- '55.5 o%>. #he sa$-le is heated9 allowing so$e of the $olecules to esca-e fro$ the li:uid into the gas -hase. I$-urities with $uch higher boiling -oints will re$ain in the distillation -ot. .s the 6a-orized sa$-le =$inus i$-urities> is cooled in the condenser9 it returns to the li:uid -hase. #he -urified li:uid is collected in the round botto$ flas! at the botto$ of the a--aratus. If si$-le distillation was used to se-arate a 35I35 $i2ture of cyclohe2ane =b- 85.8 o%> and toluene =b- ''5.6 o%>9 the first fraction of distillate would be $ostly cyclohe2ane9 but so$e toluene would be -resent. #he $aterial left in the -ot would be $ostly toluene. #he distillate would ha6e increasing a$ounts of toluene and decreasing a$ounts of cyclohe2ane as the distillation continued. If the distillate is se-arated into fractions and re/distilled9 the early fractions =lower boiling -oints> will lead to -urer cyclohe2ane9 and the late fractions will lead to -urer toluene. In situations li!e this one9 fractional distillation should be used. #he a--aratus for a fractional distillation =)igure 4> has a colu$n between the -ot and the still head. . series of se-arate distillations will ta!e -lace in this fractionating colu$n9 allowing the substances to be better se-arated.

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)igure 49 )ractional *istillation .--aratus #he structures of the fi6e -ossible $olecules with $olecular for$ula %6&'4 are shown below. #hey are constitutional isomers( they ha6e the sa$e $olecular for$ula9 but ha6e different ato$ connecti6ity. #his e2-eri$ent is an introduction to two i$-ortant techni:ues( )ractional *istillation and +,R S-ectrosco-y. @ou will use +,R s-ectrosco-y to structurally characterize the fi6e iso$ers with $olecular for$ula %6&'4. @ou will use distillation to se-arate a $i2ture of he2ane and 494/di$ethylbutane. )inally9 you will use +,R to deter$ine how well your distillation se-arated the two iso$ers.

hexane bp = 69

3-methylpentane bp = 64

2-methylpentane bp = 62

2,3-dimethylbutane bp = 58

2,2-dimethylbutane bp = 50

'3 General Instructions( 7e will ha6e a brief lecture on +,R s-ectrosco-y before any e2-eri$ental wor!. 7or! in -airs for this e2-eri$ent. #a!e se-arate laboratory notes and turn in se-arate lab re-orts. #he +,R uses a -owerful $agnet( lea6e credit cards and large $etal ob?ects =!eys> outside the roo$. *o not dis-ose of any che$icals down the sin!( we will be recycling the he2ane and 494/ di$ethylbutane. 3. Macroscale Fractional Distillation of a 9 He*ane 9 2:2;Dimethylbutane Mi*ture #he necessary fractional distillation a--aratus =shown in )igure 4> should be asse$bled in your hood. =7e will be using glass rings as colu$n -ac!ing $aterial.> 0e sure you note the -ositions of the cla$-s9 water hoses9 and ther$o$eter. Re$o6e the to- Gec! cla$-9 se-arate the distilling head fro$ the fractionating colu$n and condensing colu$n9 se-arate the fractionating colu$n fro$ the '55/$L round botto$ flas!. Obtain J45 $L =the e2act :uantity is not i$-ortant> of the he2ane(494/di$ethylbutane $i2ture in a graduated cylinder and -our it into the '55 $L round botto$ flas!. .dd a boiling stone. Reasse$ble the distillation a--aratus. <lace an 1rlen$eyer flas! labeled K' in an ice bath as the recei6ing flas!. #urn the water on in the cooling hoses =it only has to co$e out as a steady tric!le> and turn on the Lariac. .ll of the Lariacs are different9 but a good nu$ber to start on is 35/45 =the Lariac nu$bers control the a$ount of 6oltage9 they do not corres-ond to te$-erature>. #he distillation should dri- at a constant rate when the head te$-erature reaches 38/65M%. %ollect about 3 $L of that fraction in the first flas!. %hange recei6ing flas!s =to K4> and collect the rest of the distillate that co$es o6er at 38/65M%. 0e sure to -ut a cor! in K'. If the distillation is going -ro-erly9 the te$-erature will dro- after the first fraction has been collected. 7hen this dro- occurs9 change recei6ing flas!s =now K3>9 turn u- the Lariac '5 units9 and wait for the ne2t fraction. If things see$ to be going too slowly9 you can wra- the fractionating colu$n in alu$inu$ foil or turn u- the Lariac a little $ore. #he te$-erature of the ne2t fraction should be J85M%. %ollect the first few $L in K3 and then switch to K4 when the te$-erature see$s to ha6e stabilized. *o +O# distill to dryness =lea6e so$ething in the round botto$ flas!>F 0e sure to label and ca- the recei6ing flas!s after using the$9 otherwise the distillate will e6a-orate. <re-are +,R sa$-les of the two fractions you thin! are the $ost -ure. .fter you ha6e run the +,R;s9 -our all of the re$aining distillates and whate6er is left in the '55 $L round botto$ flas! into the container -ro6ided. 7. <C 5M0 (pectroscopy of the C8H 4 +somers 7hile one -artner $onitors the distillation9 the other will ?oin the -rofessor in the +,R roo$. 7e will discuss how sa$-les are -re-ared for +,R s-ectrosco-y9 the general features of the instru$ent9 and the basics of the software. 7e will then run the '3% +,R on so$e of the fi6e $olecules =ti$e -er$itting> abo6e. %o-ies of the s-ectra will be distributed. .fter this9 -artners will switch and the -rocess will be re-eated. C. <C 5M0 (pectroscopy of the ',o 1ure Fractions from the Distillation Once the fractional distillations are co$-lete9 you will -re-are sa$-les in %*%l3 =deuterated chlorofor$> of the two fractions you thin! are the $ost -ure and run the '3% +,R on the$. @ou will be -ro6ided with a co-y of the s-ectru$ of the original $i2ture for co$-arison. .fter your sa$-les ha6e been run9 discard the chlorofor$ solution in the container -ro6ided.

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Discussion @ou should discuss how well =based on the te$-erature and +,R e6idence> your fractional distillation se-arated the two iso$ers and what ste-s you could ta!e to i$-ro6e the distillation in the future. .lso9 you need to analyze each +,R s-ectru$ and discuss how it relates to the structure=s> of the $olecule=s>. .s an e2ercise9 draw out the structures of the iso$ers of %3&'4 and state how $any signals that each iso$er would gi6e in a '3% +,R s-ectru$.

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3ci);7ase E*traction

)igure '9 Se-aratory )unnel . widely e$-loyed $ethod of se-arating organic co$-ounds fro$ $i2tures in which they are found or -roduced is that of sol6ent/sol6ent e2traction. ,ost reactions of organic co$-ounds re:uire e2traction at so$e stage of -roduct -urification. In its si$-lest for$9 e2traction results fro$ the une:ual distribution of a solute between two i$$iscible sol6ents. #he distribution can be e2-ressed :uantitati6ely in ter$s of the distribution coefficient G9 using the e:uation shown below for co$-ound . distributed between an organic sol6ent and water.
K =

[ A] org [ A] aq

If the solute is co$-letely soluble in the organic sol6ent and co$-letely insoluble in water9 then G will ha6e a 6alue of infinity. #his situation is ne6er actually attained9 but any 6alue of G other than '.5 indicates that the solute is $ore soluble in one of the two sol6ents. 7hen choosing a sol6ent syste$ for an e2traction9 so$e general -rinci-les should be !e-t in $ind. ='> #he sol6ents $ust be i$$iscible. =4> #he sol6ents $ust ha6e a fa6orable distribution coefficient for the co$-onent to be se-arated. =3> #he sol6ents $ust not react che$ically with the co$-onents of the $i2ture9 e2ce-t in the cases of acid and base e2traction9 discussed below. =4> #he sol6ent $ust be readily re$o6ed fro$ the solute following e2traction. Organic acids and bases can be se-arated fro$ each other and fro$ neutral co$-ounds by e2traction using a:ueous solutions of different -&. ,ost organic acids =e.g.9 carbo2ylic acids> are insoluble or slightly soluble in water9 but these co$-ounds are highly soluble in dilute a:ueous sodiu$ hydro2ide because the organic acid reacts with the base9 as shown in e:uation '. R%O4& N +aO& R%O4/ +aN =water soluble salt> N &4O =e:. '>

#hus9 the acid $ay be selecti6ely re$o6ed fro$ a $i2ture by dissol6ing the $i2ture in an organic sol6ent li!e dichloro$ethane =%&4%l4> and then e2tracting the solution with dilute

'6 sodiu$ hydro2ide. #he organic acid $ay be reco6ered fro$ the a:ueous solution by acidification =e:. 4>9 which causes -reci-itation9 followed by filtration. R%O4/ +aN N &%l R%O4& =s> N +a%l =e:. 4>

Li!ewise9 organic bases which are insoluble in water $ay be se-arated by e2traction with dilute hydrochloric acid. #hese bases =li!e a$ines> are soluble in acid due to the for$ation of a soluble salt9 e:. 3. R+&4 N &%l R+&3N %l/ =water soluble salt> =e:. 3>

.fter the a$ine has been re$o6ed9 it $ay be reco6ered fro$ the a:ueous solution by treat$ent with base9 e:. 4. R+&3N %l/ N +aO& R+&4 =s> N +a%l =e:. 4>

,ost $acroscale e2tractions are carried out using se-aratory funnels. ,icroscale e2tractions9 on the other hand9 are con6eniently -erfor$ed with conical 6ials or centrifuge tubes using dis-osable -i-ettes to se-arate the li:uid -hases.
NH2 O OH Br benzoic acid naphthalene para-bromoaniline

E*perimental 1roce)ure 7eight out 5.4 gra$s of a solid $i2ture containing e:ual :uantities of ='> benzoic acid =%6&3%O4&>9 =4> -/bro$oaniline =0r/%6&4+&4>9 and =3> na-hthalene =%'5&8>. *issol6e the $i2ture in 4 $L of dichloro$ethane in your 3 $L conical 6ial9 war$ing slightly on the hot -late if necessary. .dd 4 $L of 6 , +aO&9 ca- the 6ial9 and sha!e it 6igorously. nscrew the ca- slightly to 6ent =release the -ressure that builds u-> the 6ial. .llow the two -hases to se-arate co$-letely. =@ou should see two distinct layers.> sing a dis-osable -i-ette9 re$o6e the lower organic layer and transfer it to a se-arate flas!. #hen re$o6e the u--er layer and sa6e it in a container $ar!ed a:ueous base e2tract. <ut the organic layer bac! into your conical 6ial and re-eat the e2traction. %o$bine the two a:ueous base layers and sa6e the$. @ou will reco6er the organic acid fro$ this a:ueous base e2tract. .dd 4 $L of 6 , &%l to the organic layer in the conical 6ial9 carrying out an e2traction li!e you did with the a:ueous base. <ut the a:ueous acid in another flas! and re-eat the -rocedure with a second 4 $L of acid. %o$bine the two a:ueous acid layers and sa6e the$ to reco6er the organic base fro$ this a:ueous acid e2tract.

'8 .dd ' $L of fresh dichloro$ethane to the organic layer in the conical 6ial. Re$o6e any traces of water by adding a s$all a$ount of anhydrous sodiu$ sulfate9 swirling the $i2ture until the solution is no longer cloudy. Se-arate the li:uid fro$ the solid by $eans of a filter ti-i-ette. @ou should now ha6e three se-arate solutions( ='> a:ueous base e2tract containing organic acid9 =4> a:ueous acid e2tract containing organic base9 and =3> organic solution containing neutral organic co$-ound. %ool the a:ueous base e2tract in ice and then neutralize it by adding 6 , &%l gradually with stirring until it is ?ust acidic with lit$us -a-er. #his neutralization will re:uire 4/4 $L of &%l. .n insoluble solid should be obser6ed at this -oint. If you do not see a solid9 you $ay need $ore &%l or you $ay need to cool your sa$-le further. Isolate the solid by 6acuu$ filtration using a &irsch funnel9 and wash the solid with a small a$ount of col) water. Let the solid dry in a sa$-le 6ial o6ernight before deter$ining its weight and $elting -oint. Re-eat the abo6e -rocedure on the a:ueous acid e2tract using 6 , +aO&. .fter you isolate this solid9 allow it to dry o6ernight in a labeled sa$-le 6ial before obtaining its weight and $elting -oint. 16a-orate the dichloro$ethane fro$ the organic layer by boiling off the sol6ent on a hot-late in the hood. +ote that dichloro$ethane boils at a 6ery low te$-erature9 so your hot -late only needs to be war$. 7hen $ost of the li:uid has e6a-orated9 allow the sa$-le to cool so that the organic neutral co$-ound will crystallize. =+ote that the neutral organic co$-ound $ay $elt and a--ear as a li:uid on the hot-late.> Let the solid dry o6ernight in a sa$-le 6ial before deter$ining its weight and $elting -oint. 0esults( ='> Include a flow chart to describe the se-aration of the $i2ture and the isolation of each co$-onent. =4> %alculate the -ercent reco6ery of each co$-onent in the $i2ture. .ssu$e that each co$-onent was -resent in e:ual a$ounts in your sa$-le. =3> %o$-are the $elting -oints of each sa$-le you isolated with their literature $elting -oints =obtained fro$ a %R% &andboo!>. =4> %o$$ent on the -urity of each reco6ered co$-onent. =3> &ow could the se-aration and reco6ery of the co$-ounds se-arated be i$-ro6edE =uestions( ='> *uring an e2traction9 if you beco$e uncertain about which layer is the organic layer9 how could you deter$ine it e2-eri$entallyE =4> )ro$ the results of this e2-eri$ent9 what can you conclude about the solubilities of each co$-onent in your $i2tureE 7rite specific che$ical e:uations for each reaction that too! -lace9 using the s!eletal structures of the $olecules =3> Should it $a!e any difference if the $i2ture is e2tracted first with &%l or +aO&E 12-lain. =4> <ro-ose a $ethod to se-arate a $i2ture containing -henol9 benzoic acid9 na-hthalene9 and -/bro$oaniline. <henol is soluble in sodiu$ hydro2ide solution but insoluble in neutral water or sodiu$ bicarbonate solution. 0enzoic acid is soluble in either sodiu$ hydro2ide or sodiu$ bicarbonate solutions. 7rite out the structures of the $olecules in your sche$e.

'8

Chromatography
7ac%groun) Read << 446/8 in ,c,urry te2t as well as the chro$atogra-hy section on the organic che$istry web -age. #he dyes you will be se-arating include( fluorescein =yellow>9 bro$ocresol green =yellow/green>9 $ethyl red =red>9 basic fuchsin =-ur-le red>9 rhoda$ine 0 =-in!>9 and new $ethylene blue =blue>9 with their structures shown below.

Dyes 1roce)ure' sing a nu$ber 4 -encil9 $ar! your #L% -late with e6enly s-aced dots about ' c$ fro$ the botto$9 to clearly delineate where each dye solution will be s-otted. )or later reference9 nu$ber these s-ots to clearly note where each solution was s-otted. sing a fresh '/L $icro-i-et for each solution9 each of the dye standards and the un!nown will be s-otted at one of the labeled s-ots. .fter s-otting the solutions on the #L% -late9 allow the -late to dry before -lacing it in the de6elo-ing cha$ber. *e6elo- the -late using 4/-ro-anolIacetic acid ='3 ( 4 6I6>9 $a!ing sure that the de6elo-ing cha$ber has had ti$e to e:uilibrate ade:uately. 7hen the dyes are well se-arated9 re$o6e the -late fro$ the cha$ber and immediately $ar! the sol6ent front with a -encil. Once the #L% -late is dry9 deter$ine the RfHs of each co$-ound. .lso9 deter$ine the co$-osition of your un!nown by co$-aring it to the !nown standards that you ran. <re-are a chro$atogra-hic colu$n by inserting a s$all -lug of glass wool into the nec! of a " in dis-osable -i-et. #he glass wool should be gently but fir$ly -ac!ed in the botto$ end of the -i-et and then co6ered with a thin layer of sand. .dd a--ro2i$ately 835 $g of silica gel to the colu$n9 -ac!ing it by gently ta--ing the outside wall of the -i-et with a -encil. <re-are the colu$n for de6elo-$ent by washing the silica gel with one 6olu$e of eluting sol6ent =waterI'/-ro-anolIacetone9 ' ( ' ( '>. #he dye $i2ture you will be se-arating contains fluorescein and new $ethylene blue in ethanol =' $g of each dye -er $L of ethanol>. .dd two dro-s of the dye solution carefully to the to- of the silica gel. 7hen the li:uid le6el has dro--ed to the to- of the silica gel9 a--ly a thin layer of sand to the to- of the colu$n. )ill the colu$n to the to- with the eluting sol6ent. #he sol6ent le6el $ust be !e-t abo6e the to- of the silica gel throughout the e2-eri$ent by continuously adding sol6ent. #he co$-onents of the $i2ture se-arate :uic!ly as they $o6e down the colu$n. #he fluorescein will elute fro$ the colu$n ra-idly. @ou will need to change your eluting sol6ent to waterI'/ -ro-anolIacetoneIacetic acid ='('('('> in order to obtain the new $ethylene blue. %ollect the se-arated dyes in indi6idual 6ials and analyze the$ by #L% to deter$ine how effecti6e your colu$n se-aration was. =uestions

'

Reynolds9 R. %.C O;*ell9 %. .. J !hem Ed. !!49 ""9 "8".

'" ='> %onstruct a table of dyes and Rf;s. 0ased on your #L% results9 ran! the dyes in ter$s of -olarity//least to $ost -olar. 12-lain your ran!ing. =4> 7hy does the fluorescein elute $ore ra-idly fro$ the colu$n than the new $ethylene blueE =3> &ow effecti6e was your colu$nE 12-lain. E*ercise 0enzoic acid and na-hthalene =see structures fro$ -re6ious lab> can be se-arated on a silica gel #L% -late. .lthough they are both colorless9 ultra6iolet light will re6eal their -ositions on a #L% -late. . student had a dichloro$ethane solution of benzoic acid and na-hthalene and s-otted three silica gel #L% -lates with the solution. One #L% -late was de6elo-ed in he2ane9 the ne2t in '(' he2ane(acetone9 and the last in -ure acetone. nfortunately9 the -lates were $i2ed u-9 but are shown below. 0ased on your understanding of chro$atogra-hy9 -erfor$ the following tas!s( =a> Label the s-ots on each #L% -late with a 7 for benzoic acid and an 5 for na-hthalene. =b> Identify the sol6entIsol6ent $i2ture for each -late. =c> <ro6ide an e2-lanation for your answers.
finish finish finish

start

start

start

solvent____________

solvent____________

solvent____________

Chemical (hift an) +ntegration in the 5M0

Reading( --. 434/4689 488/484 in ,c,urry te2t. )or this e2-eri$ent we will be e2a$ining a--ro2i$ately '5 co$-ounds by '3% andIor '& +,R. #his wee! we will be focusing on the che$ical shift of the signals in the +,R and the reasons for the che$ical shift. 7e will also use '& +,R to deter$ine the nu$ber of hydrogens that gi6e rise to a signal. #he co$-ounds we will be e2a$ining are shown below9 grou-ed based on the ty-e of +,R =carbon or -roton> we will be using. 7e $ay study a few of the co$-ounds by both ty-es of +,R. .s a -re/lab e2ercise9 deter$ine the nu$ber of carbon signals in each co$-ound in the first set. #hen deter$ine the nu$ber of -roton signals in the second set. #he easiest way to show the nu$ber of different signals is to label the different carbons or hydrogens with lower case letters. )or e2a$-le9 '/bro$ohe2ane has si2 carbon signals and the structure has been labeled a/f. If the carbonsIhydrogens are the sa$e9 they get the sa$e letter.

45

Compoun)s for <C 5M0

O Br a c e OH O O

six C signals

OH

O2N NO2

Compoun)s for H 5M0

OCH3 O O OCH3

4' Lab 0eport Redraw the first set of co$-ounds shown below on another sheet of -a-er. <erfor$ the following for each co$-ound( ='> State how $any signals will be seen in the '3% +,R. =4> Label the carbons in the structure with lower case letters =a9 b9 c9 etc.> corres-onding to the nu$ber of signals in the +,R s-ectru$. In other words9 if you ha6e fi6e signals9 you should ha6e fi6e different letters. If the carbons are identical9 they will ha6e the sa$e letter. =3> )or each signal9 gi6e the range of che$ical shift 6alues which are e2-ected9 using the table in your te2tboo! as a reference. .n e2a$-le(
a O b c a b c 190-200 ppm 20-60 ppm 15-40 ppm
N O O O O F

c 3 signals

O O O O N N

N N

)or the ne2t set of co$-ounds9 do the sa$e things as abo6e9 labeling all of the hydrogens. =@ou do not need to draw out each hydrogen ato$.> +n a))ition: gi2e the integration for each signal. .n e2a$-le(
c d b
Cl

a b c d

0.7-1.3 ppm 2.5-4.0 ppm 1.2-1.4 ppm 0.7-1.3 ppm

3H 1H 2H 3H O OMe
B O OH O

H O

NH

44

(pin;(pin (plitting in H 5M0 (pectroscopy

16ery '& +,R s-ectru$ we ha6e seen so far has had single -ea!s for signals. &owe6er9 in '& +,R9 unli!e '3% +,R9 the signals do not always a--ear as single -ea!s. Often9 '& signals are s-lit into see$ingly co$-le2 -atterns. #his e2-eri$ent will be an introduction to the -heno$enon called s-in/s-in s-litting. @ou need to read section '3.8 and '3.8 in your ,c,urry te2tboo!. <ay careful attention to rules on -. 48' and #able '3.4 on -. 484. 7e will be $ore concerned with the -ractical conse:uences and not so $uch the theory of s-in/s-in s-litting. 6eneral +nstructions9 7e will loo! at a few s-ectra that de$onstrate different si$-le s-litting -atterns. 1ach student will $a!e u- an +,R sa$-le of one of the co$-ounds below and run its s-ectru$. 7e will loo! at so$e e2a$-les of co$-le2 s-litting -atterns
O O O O 2-butanone 3-methyl-2-butanone 4-methyl-2-butanone butyraldehyde (butanal) Cl

OH NO2 benzyl alcohol NO2 p-nitrotoluene Ha Hb styrene Hc m-nitrotoluene

NO2

O O

o-nitrotoluene

piperonal (piperonaldehyde)

0eport )or the s-ectru$ that you obtained in lab9 do the following( ='> *raw the s!eletal structure of the co$-ound. =4> Label the different &;s on the co$-ound using lower case letters. =3> Label each signals on the s-ectru$ with the letter corres-onding to the ty-e of hydrogen. =4> 0ased on the structure you drew9 discuss how the e2-ected che$ical shift and integration $atch what you obser6e on the s-ectru$.

43 =3> 0ased on the structure you drew9 -redict how each signal should be s-lit. %o$-are your -redictions with the s-ectru$ and account for any a--arent discre-ancies.
OMe

)or 4/6inylanisole =structure shown below>(

='> =4>

*o the sa$e !ind of analysis that you did for the s-ectru$ you obtained in lab9 described abo6e. #he al!ene -roton region has been e2-anded and the cou-ling constants shown. *raw out a :ualitati6e tree diagra$ si$ilar to the one shown on -. 483 of the ,c,urry te2tboo!.

)or the three un!nown co$-ounds( <ro-ose -lausible structures for each of the un!nown co$-ounds based on their +,R s-ectra and che$ical for$ulas. #he -ossible functional grou-s are shown on the inside co6er of your ,c,urry te2t. .fter you ha6e -ro-osed a structure9 you should analyze it li!e you did the -re6ious s-ectra in order to chec! your answer. #he che$ical shift9 integration9 and s-litting of the should be consistent with the -redicted 6alues for your -ro-osed structure. #urn in all labeled s-ectra with your re-ort.

44

Caffeine
In this e2-eri$ent9 caffeine is isolated fro$ tea lea6es. #he chief goal is to se-arate caffeine fro$ the other co$-onents in the tea lea6es. #ea lea6es9 li!e other -lants9 consist $ainly of cellulose. %ellulose is a -oly$er of glucose =structure shown below>. %ellulose is insoluble in al$ost e6ery co$$on sol6ent9 including water. %affeine is water soluble and constitutes as $uch as 3D by weight of tea lea6es. #annins are another class of co$-ounds found in tea9 and they are water soluble. #annins ha6e the -henol functional grou-. So$e tannins are hydrolyzed in hot water to -roduce gallic acid. #annins and gallic acid are both acidic due to their -henol grou-s and carbo2ylic acid grou-9 res-ecti6ely. #he last co$-onents of tea to worry about are fla6onoid -ig$ents and chloro-hyllsC these colored co$-ounds gi6e tea its brown color. %hloro-hylls and caffeine are both soluble in $ethylene chloride9 but $ost other substances in tea are not.
O &3% + + %& 3 %affeine Glucose if R O & . tannin if so$e R O *igalloyl %& 3 + + RO RO RO %& 4 OR O

OR

O O

O O& &O

O O&

O& O& . digalloyl grouO&

O& O& Gallic .cid

O&

1re;Lab E*ercise Gi6en the infor$ation abo6e9 construct a flow chart based on the -rocedure below showing how caffeine is isolated fro$ the other co$-onents of tea. In other words9 what ha--ens to the cellulose9 tannins9 gallic acid9 fla6onoids9 and chloro-hyllsE 1roce)ure' <lace 4 g of blac! tea lea6es9 '3 $L of dichloro$ethane9 and 3 $L of 5.4 , +aO& in a 35 $L 1rlen$eyer flas!. %or! the flas! and swirl it for 8 $inutes. *o not sha!e the flas! 6igorously9 or the $i2ture will for$ an e$ulsion.

'

Ona$i9 #.C Ganazawa9 &. J !hem Ed. !!69 #39 336.

43 Se-arate the dichloro$ethane fro$ the wet tea lea6es by 6acuu$ filtration with a fritted glass funnel. =@ou $ay also use a 0uchner funnel with 3 g of %elite.> 7ash the lea6es with an additional -ortion of dichloro$ethane. %o$bine the two dichloro$ethane solutions and dry the$ with anhydrous sodiu$ sulfate. Re$o6e the sol6ent by rotary e6a-oration. *issol6e the slightly green solid in ' $L of dichloro$ethane and rinse it into a test tube using a filter ti- -i-et to re$o6e any insoluble i$-urities9 using another ' $L of dichloro$ethane to rinse the flas!. 16a-orate the dichloro$ethane in a water bath in the hood. <urify the crude caffeine by $i2ed sol6ent recrystallization fro$ 4/-ro-anol and he2ane. *issol6e the sa$-le in a $ini$u$ a$ount of hot 4/-ro-anol9 adding he2ane until a faint cloudiness a--ears. .llow the $i2ture to cool before collecting the crystals 6ia 6acuu$ filtration. 7ash your recrystallized sa$-le with cold he2ane. .lternati6ely9 you $ay -urify the caffeine 6ia subli$ation9 using the a--aratus shown below.

subli$ation a--aratus 0eport #urn in your flow chart fro$ abo6e. %o$$ent on the -urity of the caffeine. &ow could you i$-ro6e the -rocedureE

46

Orientation to (partan
%on6entional =hand/held> $olecular $odels ha6e been =and continue to be> useful in 6isualizing $olecular structures in three di$ensions. Indeed9 they ha6e been al$ost indis-ensable for that -ur-ose9 although they are gradually and -artially being su--lanted by co$-uter based $olecular gra-hics. ,any students ha6e difficulty dealing with intra$olecular relationshi-s9 des-ite the aid of $odels. ,olecular $odels are useful for e2a$ining steric interactions but do not gi6e :uantitati6e infor$ation about steric energy. . $ore co$-lete a--roach to understanding s-atial relationshi-s and stereoche$istry is to co$bine $olecular $odels with co$-uter based $olecular $echanics calculations. #he total steric energy for the o-ti$ized geo$etry of a $olecule is -erha-s the $ost widely used -iece of infor$ation obtained fro$ a $olecular $echanics calculation. #he absolute 6alue for the steric energy 6aries fro$ -rogra$ to -rogra$ and is of little or no useC howe6er9 the relati6e size of indi6idual interactions =co$-ression9 bending9 stretch/bend9 torsional> that co$-ose the total steric energy can be hel-ful in identifying s-ecific sites and ty-es of strain. In general9 howe6er9 it is $ost infor$ati6e to co$-are steric energies and establish the relati6e stabilities of structural iso$ers9 stereoiso$ers9 and roto$ers in staggered confor$ations. #he $olecular $echanics force field is a co$-utational $odel for describing the -otential energy surface for all the -ossible $o6e$ents of ato$s within a $olecule. In so$e res-ects it is si$ilar to the fa$iliar hand/held $olecular $odels9 but it is $uch $ore so-histicated. )orce fields ha6e been -ara$eterized9 or fit9 to gi6e e2cellent geo$etries9 relati6e confor$ational energies9 heats of for$ation9 crystal -ac!ing arrange$ents9 and e6en transition state structures and reacti6ities. #he $a?or distinction between the $olecular $echanics $ethod used in this e2-eri$ent and :uantu$ $echanics is that $olecular $echanics does not consider the electrons in the $olecule e2-licitly. ,olecular $echanics treats the ato$s and their associated electrons as units interconnected by the -otential functions that we ha6e described. On the other hand9 :uantu$ $echanics is 6ery $uch concerned with the three di$ensional distribution of electrons around the nuclei. 7ith $olecular $echanics9 steric hindrance9 confor$ation9 bond angle defor$ation9 etc.9 can be addressed in a :uantitati6e $anner. #his a--roach su--lants $any of the hand/ wa6ing argu$ents based u-on hand/held $odels that one ty-ically finds in the classroo$. 0ecause s$all changes in structure can lead to large changes in total energy9 calculations to deter$ine o-ti$u$ geo$etry are iterati6e. #he energy and its first deri6ati6e with res-ect to all geo$etrical coordinates are calculated for the starting geo$etry9 and this infor$ation is then used to -ro?ect a new geo$etry. #he -rocess needs to continue until the or o-ti$ized geo$etry =with the lowest energy> is reached. Geo$etry o-ti$ization does not guarantee that the final structure has a lower energy than any other structure of the sa$e $olecular for$ula. .ll that it guarantees is a local $ini$u$9 that is9 a geo$etry with an energy lower than that of any si$ilar geo$etry.

'

&ehre9 7. B.C 0ur!e9 L. *.C Shuster$an9 .. B. A Spartan $utorialC 7a6efunction( Ir6ine9 %.9 '""3.

48 (tarting (partan #y-e S-artan PenterQ in the +IR shell window. -sing (partan (oft,are ='> ,ouse se in S-artan S-artan uses a consistent way of interacting with the $olecules on screen. )or the sa!e of con6enience9 the $ouse use is described in the table below. #he s-acebar $odifier wor!s only in the $olecule building $ode =the only $ode in which you can -ic! bonds> where SrotationT rotates one of the two frag$ents lin!ed by the selected bond and StranslationT lengthens or shortens the bond. Since it is -ossible to ha6e $ore than one $olecule in the $ain window9 the so/called global $ani-ulation in the table below refers to the o-eration being -erfor$ed on all $olecules at the sa$e ti$e. In the global rotation case9 an o-tion e2ists in the S-artan ,enu =under <references> to rotate around the global center or rotate each $olecule around its own center. 'able 9 -se of the mouse button in (partan left $ouse button $iddle $ouse button right $ouse button $odifier !ey=s> =-ic!ing> =rotation> =translation> none 2y rotation 2y translation shift z rotation z translation ctrl N shift global z rotation global z translation =4> ,olecule Selection. .s $any $olecules as desired $ay be si$ultaneously dis-layed in S-artan;s $ain window. &owe6er9 only one $olecule $ay be selected. #he selected $olecule has access to all $enu functions =$olecule building9 ?ob setu- and sub$ission9 etc.>9 while non/ selected $olecules $ay only be dis-layed as static i$ages. =3> 0uilding ,olecules. 0uilding a $olecule with S-artan wor!s in a si$ilar way as building a $olecule using a $odel !it. @ou first select an ato$ =and its hybridization> or a -rebuilt grou-9 which you then -lace in the window. )ro$ then on you add new ato$s or grou-s to $a!e bonds fro$ the o-en 6alences of the $olecule under construction. Lalences that are left o-en when e2iting the builder $ode will auto$atically be filled with hydrogen ato$s. #here are three le6els for building $olecules. #he S1ntryT le6el contains easy access to $ost co$$only used ele$ents and hybridization as encountered in organic che$istry. #he S12-ertT le6el -ro6ides a larger selection of ato$s and hybridizations9 and allows you to select the !ind of bond =single9 double9 tri-le9 delocalized>. LetHs start with the entry/le6el builder and build as-irin9 which has the structure shown below.
O OH O O CH3

#o start building a new $olecule select File9 5e,. #his will o-en the 0uilder window and a frag$ent -anel. #he frag$ent -anel consists of three $a?or -arts( toato$ ty-es and hybridizations center frag$ent selection for grou-s or rings botto$ builder $ode selection buttons and so$e editing functions for ato$s and bonds

48 In the frag$ent -anel9 chec! the bo2 labeled 0ings9 and clic! on the drawing to dis-lay the -o-u- $enu9 fro$ which you choose the ring that you want. =In this case9 the default choice9 -henyl9 is the one you want.> %lic! anywhere in the blac! builder window to -osition the -henyl ring as the starting bloc! for the structure. +e2t we will build the carbo2ylic acid grou- =%O4&> fro$ single ato$s. )ro$ the to- -art of the frag$ent -anel9 select the s-4 hybridized carbon and attach it to the -henyl by clic!ing on any of the free 6alences of the -henyl ring. @ellow/ended lines show the free 6alences. Select the s-3 hybridized o2ygen =the one with two single bonds> and attach that to the single bond of the carbon9 then select the s-4 o2ygen and attach that to the double bond on the carbon. #o add the ester grou- we will use the -redefined functional grou-s. %hec! the 6roups chec!bo2 in the frag$ent -anel and fro$ the list of grou-s =-o-u- $enu> select Ester. #he 6alence that will be used in the attach$ent to the e2isting frag$ent is labeled with a little circle. +otice that this grou- has two different free 6alences. #o change the attach$ent -oint9 clic! on the little -ictorial re-resentation of the ester. sing this a--roach9 attach the o2ygen end of the ester grou- to the -henyl grou-9 at the carbon ne2t to the one containing the carbo2ylic acid grou-. #o co$-lete the ester grou-9 select the s-3 hybridized carbon and attach it to the other side of the ester grou-. @ou $ay want to rotate the $olecule to get better access to the free 6alence that you want to add to9 or ?ust to change the 6iew. In the builder window hold the $iddle $ouse button down and drag the $ouse to rotate the structure =this is called Sclic! and dragT>. +ow that you ha6e built the $olecule9 there are a cou-le of additional ste-s to finish the ?ob. Select ,ini$ize fro$ the botto$ -art of the frag$ent -anel in order to do a si$-le ,, energy o-ti$ization9 using #ri-os 3.4 force field. +otice that when the structure is o-ti$ized to $ini$ize the energy9 a dialog bo2 gi6es you so$e infor$ation regarding the $ini$ization -rocess and the sy$$etry of the $olecule. %lic! OG when you finish reading the infor$ation. #o sa6e the $olecule9 select File9 (a2e9 and fill out a na$e for the $olecule9 e.g.9 as-irin. #o e2it the builder and return to the $ain window9 select File9 =uit. =@ou actually could ha6e selected File9 =uit without first sa6ing the structure and the -rogra$ would ha6e as!ed you whether you wanted to sa6e the $olecule or not.> Displaying the Mo)el .fter e2iting the builder9 the $olecule is dis-layed in the $ain window. #he $olecule is the SselectedT $olecule9 i.e. the one on which o-erations will be -erfor$ed. #he title bar of the window shows the na$e of the selected $olecule together with a se:uence nu$ber. In this case9 the window would show as-irin =5>. +otice that a coloring sche$e is used to cue you 6isually as to which ato$ is which in the structure. #here are different ways in which you can ha6e the $olecule dis-layed. #hese can be selected fro$ the ,odel $enu. Loo! at the o-tions gi6en in the ,odel $enu. Labeling only wor!s when the $olecule is 6iewed in one of the two wire $odes. &ide is really only useful when you are

4" loo!ing at calculated surfaces or 6olu$es and you donHt want the $odel drawing to interfere. =@ou will use the hide function later.> #ry each of the dis-lay $odels9 listed below9 to see what the $olecule loo!s li!e in each dis-lay $ode. wire ball and wire tube ball and s-o!e s-ace filling Loo! at the $olecule without the hydrogens in these $odes by selecting Mo)el9 Hi)e Hy)rogens =to turn the dis-lay of hydrogens bac! on9 select Mo)el9 (ho, Hy)rogens>. Loo! at the $olecule with the labels on by selecting Mo)el9 (ho, Labels =to turn the labels off9 select Mo)el9 Hi)e Labels>. #he labels will only be shown in the 7ire or 0all and 7ire dis-lay $odes. #ry to rotate and translate the $olecule. =See #able ' abo6e or on/line hel-.> #ry to rotate around one bond in the $oleculeC re$e$ber that you can only do this in the editor9 so select 7uil)9 E)it (tructure as your first ste-. 7hen you are finished9 re$o6e the $olecule fro$ the window by selecting File9 Close. =4> Sub$itting Bobs. Select a calculation $ethod fro$ the (etup $enu. %lic! inside the 'itle bo2. #y-e a suitable na$e for your $olecule. =#his na$e will be re-roduced in the te2t out-ut.> Select an a--ro-riate tas! =e.g.9 Geo$etry O-ti$ization> fro$ the 'as% $enu. 7hen you are finished9 clic! on sa6e to e2it the dialog. Select (ubmit fro$ the (etup $enu. 7hen the calculation has co$-leted you will be notified.

35

(partan E*ercise. 0otational 7arriers in 3l%anes

&ow $uch energy does it ta!e to rotate around the %/% bond in ethaneE 7hat ha--ens to this energy if a $ethyl grou- re-laces one of the -rotonsE =7eHre co$-aring the bond rotation energy of ethane and -ro-ane here.> 7hat ha--ens to this energy if two -rotons on different carbons are re-laced by $ethyl grou-sE =&ere9 weHre co$-aring the bond rotation energy of ethane and butane.> In order to answer these :uestions9 set u- coordinate dri6ing calculations for the <,3 $ethod using the geo$etry o-ti$ization tas!. 0uild ethane and -erfor$ a geo$etry o-ti$ization using the <,3 $ethod. #o carry out the coordinate dri6ing calculations9 select 7uil)9 Coor)inate Dri2ing. #his o-ens the coordinate dri6ing -anel9 where you can in-ut the geo$etric -ara$eters that you want to syste$atically change. %lic! on the Define Dihe)ral button in the %oordinate *ri6ing <anel9 and select four ato$s or three ad?acent bonds. #he four ato$s you choose should ha6e the sa$e relationshi- as the ato$s circled below in the structure for ethane. +ote that in the +ew$an -ro?ection shown below9 the two hydrogens are enclosed in bo2es. #he hydrogens and the carbon ato$s they are attached to are the four ato$s you should 6ary. .fter you choose the four ato$s9 the calculated dihedral angle will dis-lay in the bo2. @ou can !ee- the current nu$ber in the from bo2 and use the current dihedral angle -lus '85 for the to bo2. #hirteen ste-s should be sufficient for the coordinate dri6ing. Sa6e the %oordinate *ri6ing choices and e2it that dialogue. #hen sub$it the calculation to do the coordinate dri6ing.
H
H H

H
H H

H H

7hen the calculation is co$-leted9 you will ha6e a list of $olecules. *raw each confor$er9 indicating the relati6e relationshi-s of the grou-s around the central carbons. 7ith each confor$er9 indicate the energy calculated by the coordinate dri6ing calculation. 7ith this infor$ation9 you should be able to draw a gra-h that shows energy with res-ect to rotation around the %/% bond. Re-eat this -rocess for butane9 $a!ing sure to choose the central %/% bond as the $iddle two ato$s of the four. @our first and last ato$s should be the first and fourth carbons in the chain. *raw a gra-h showing the energies of these confor$ations as a function of bond rotation.

3'

Conformations of Molecules
In this e2-eri$ent you will use Lariable #e$-erature +,R and S-artan ,olecular $odeling to e2a$ine the confor$ations of an a$ide and substituted cyclohe2anes. Variable Temperature NMR !a " #. $%"a"i%n %& amides #he '& +,R s-ectru$ of di$ethylfor$a$ide consists of three singlets at roo$ te$-erature( the two $ethyl grou-s are ine:ui6alent due to a significant contribution of the resonance structure shown below. .t higher te$-eratures9 enough energy is -resent to o6erco$e the %/+ rotational barrier and the two $ethyl grou-s a--ear as one singlet. 7e will use 6ariable te$-erature +,R to deter$ine the te$-erature at which the two $ethyl grou-s a--ear e:ui6alent =coalescence te$-erature>. @ou will co$-are those results to other a$ides li!e di$ethyl benza$ide.
O CH3 H N CH3 H N CH3 O CH3

3nalysis of 5M0 results @ou can calculate the rate constant of rotation using the following e:uation9 % c = 4.44 where %c is the rate constant at the coalescence te$-erature and is the distance in &z between the two signals at low te$-erature. #he barrier to rotation =in BI$ol> is calculated with the following e:uation9 $c barrier = '".'4$c '5.34 + log % c where $c is the coalescence te$-erature =in Gel6in> and %c was calculated abo6e. 7ith di$ethylbenza$ide9 we found a coalescence te$-erature of 45 o% and the distance between the signals at low te$-erature was 4'.48 &z. In another e2-eri$ent with di$ethyl formami)e9 the coalescence te$-erature was '85 o% and the distance between the signals was 35.4 &z. !a " B. C'cl%(e)ane C(ai -C(ai *n"e c%n+e si%ns. #he '& +,R s-ectru$ of cyclohe2ane consists of one singlet at roo$ te$-erature. .ll of the -rotons a--ear e:ui6alent because there is enough energy at roo$ te$-erature to o6erco$e the ring fli- energy barrier. .t low te$-eratures9 there is not enough energy to fli- between chair confor$ations and two signals a--ear9 corres-onding to the a2ial and e:uatorial -rotons. =See -.
'

.!itt9 B. 7. &M' and !hemistry( An )ntroduction to Modern &M' SpectroscopyC %ha-$an and &all( London9 '""4.

34 465 in your lecture te2t.> 7e will use 6ariable te$-erature +,R to e2a$ine this beha6ior in bro$ocyclohe2ane and cyclohe2anol. 7e will focus s-ecifically on the signal of the -roton bonded to the sa$e carbon as the R grou- =0r or O&>. #he results will be co$-ared to cyclohe2ane and correlated with S-artan calculations of the energy barriers.
X H

X = Br or OH
3nalysis of results. In order to deter$ine the free energy difference between the two chair confor$ations9 you first need the e:uilibriu$ constant9 G9 for the intercon6ersion9

K=

[ conformation A ] [ conformation* ]

where the concentration of each confor$ation is gi6en by integrating their res-ecti6e signals at low te$-erature. )ro$ our data at U85 o%9 the two integrals ga6e a ratio of 3.3" ( '. #he difference in free energy is then deter$ined with the following ther$odyna$ic e:uation9 where R9 the gas constant9 is e:ual to 8.3'3 for this e2a$-le>. 1art ++. (partan2 In this e2-eri$ent9 se$i/e$-irical .,' calculations are used to assign and inter-ret confor$ational -references in an a$ide and in two substituted cyclohe2anes. Substituted cyclohe2anes -refer a confor$er in which the substituent grou- is e:uatorial. #he e:uatorial confor$er of $ethylcyclohe2ane is lower in energy than the a2ial confor$er9 and the e:uatorial/a2ial difference increases as the substituent gets larger.
J and # is the te$-erature in Gel6in ='"3 G mol K

$ $ e,-a"% ial

$ $ a)ial

%onfor$ational -references in disubstituted cyclohe2anes can be -redicted by si$-ly adding together the energies fro$ the indi6idual substituents on the ring. Significant de6iations fro$
4

&ehre9 7. B.C Shuster$an9 .. B.C &uang9 ,. 7. A Laboratory *oo% of !omputational Organic !hemistryC 7a6efunction( Ir6ine9 %.9 '""6.

33 additi6ity indicate interactions between substituents. )or e2a$-le9 direct steric interaction between al!yl substituents in a '93/dia2ial confor$er $ight gi6e an es-ecially large -reference for the e:uatorial confor$er.
s"e ics
$

$ $

Procedure 1art 3. Dimethylformami)e (DMF) 0uild *,) and -erfor$ a geo$etry o-ti$ization using the <,3 $ethod. #o carry out the
CH3
H O N CH3

coordinate dri6ing calculations9 select 7uil)9 Coor)inate Dri2ing. #his o-ens the coordinate dri6ing -anel9 where you can in-ut the geo$etric -ara$eters that you want to syste$atically change. %lic! on the Define Dihe)ral button in the %oordinate *ri6ing <anel9 and select four ato$s or three ad?acent bonds. #he four ato$s you choose should be the carbon and o2ygen in the carbonyl grou-9 the nitrogen9 and one of the $ethyl grou-s. .fter you choose the four ato$s9 the calculated dihedral angle will dis-lay in the bo2. @ou can !ee- the current nu$ber in the from bo2 and use the current dihedral angle -lus '85 for the to bo2. #hirteen ste-s should be sufficient for the coordinate dri6ing. Sa6e the %oordinate *ri6ing choices and e2it that dialogue. #hen sub$it the calculation to do the coordinate dri6ing. Re-eat these ste-s for benza$ide. 3nalysis of results. 7hen the calculation is co$-leted9 you will ha6e a list of $olecules. *raw a +ew$an -ro?ection for each confor$er9 indicating the dihedral angle of the grou-s. 7ith each confor$er9 indicate the energy calculated by the coordinate dri6ing calculation. 7ith this infor$ation9 you should be able to draw a gra-h that shows energy with res-ect to rotation around the %/% bond. 1art 7. (ubstitute) Cyclohe*anes. 0uild e:uatorial and a2ial bro$ocyclohe2ane9 o-ti$ize using the .,' se$i/e$-irical $ethod9 and calculate and record the heats of for$ation for both confor$ers. %o$-are the energies =heats of for$ation> for the e:uatorial and the a2ial confor$ers. 12a$ine the o-ti$ized geo$etries9 drawing each of the$. +ote in -articular the dihedral angles between the bro$ine ato$ and carbons 3 and 3 in the ring. Lab 0eport !a " #. #mides *iscuss why there is a barrier to rotation around *,) =and benza$ide> and $olecules li!e it. 5M0. 12-lain how the +,R e6idence shows the barrier to rotation. %alculate the rate constant and barrier to rotation for both di$ethylbenza$ide and di$ethylfor$a$ide.

34 (partan. )ro$ your gra-h9 deter$ine the energy barrier for this rotation. &ow does this energy barrier co$-are to the barrier to rotation in ethaneE in butaneE Comparing metho)s. %o$-are the barrier to rotation 6alues obtained by the different $ethods =+,R and S-artan>. 12-lain why di$ethylfor$a$ide has a higher barrier to rotation that di$ethylbenza$ide. It $ight hel- to consider resonance structures which in6ol6e the aro$atic ring. !a " B. C'cl%(e)anes 7hich is the $ore stable confor$ationE 7hyE 5M0. 12-lain how the +,R s-ectra show the different confor$ations of bro$ocyclohe2ane. *iscuss how the +,R is changing as the te$-erature is lowered and what those changes indicate about the co$-ound. %alculate the difference in free energy between the two confor$ations. (partan. %alculate the difference in energy between the two different confor$ations you built. Comparing metho)s. %o$-are the free energy differences obtained with the two different $ethods.

33

Competiti2e 5ucleophiles &ith ;7utanol

In this e2-eri$ent you will deter$ine the nucleo-hile strength of bro$ide ion 6s. chloride ion in their reaction with '/butanol in acidic solution. #he reaction is shown below. #he reagents are a con6enient source of &0r and &%l. #he reaction is an S+4 reaction with &4O as the lea6ing grou- and %l/ and 0r/ as the nucleo-hiles. #he $olar a$ounts of %l/ and 0r/ are e:ual9 so the better nucleo-hile will lead to $ore -roduct. @ou will analyze the a$ounts of '/bro$obutane and '/chlorobutane by G% and +,R. If ti$e -er$its9 we will also e2a$ine the sa$e reaction with 4/$ethyl/4/-ro-anol.
NH4Cl, NH4Br OH H2SO4 Cl + Br

E*perimental 1roce)ure .sse$ble an a--aratus for reflu2 using a 43 $L round/botto$ flas!9 a reflu2 condenser9 and a stir bar. sing a '5/$L graduated cylinder9 obtain '5.5 $L of the sol6ent/nucleo-hile $i2ture =+&40r N +&4%l N &4SO4> which is in an 1rlen$eyer flas! in the hood. <our the $i2ture i$$ediately into the round botto$ flas!. .dd 5.83 $L of '/butanol to the round botto$ flas!9 attach the condenser9 start the water circulating and the stir bar s-inning. #urn on the heating $antle and heat the $i2ture at gentle reflu2 =loo! for the reflu2 ring in the condenser> for about one hour. .fter the heating -eriod9 lift the round/botto$ flas! fro$ the heat and allow it to cool. *o not re$o6e the condenser until the flas! is cool. @ou can i$$erse the flas! in cold ta- water to hel- it cool =don;t re$o6e the condenser>. @ou should see an organic layer at the to- of the reaction $i2ture. .dd J' $L of -entane to the $i2ture and gently swirl the flas!. #he -ur-ose of the -entane is to increase the 6olu$e of the organic layer so it;s easier to se-arate. sing a <asteur -i-et9 transfer $ost of the botto$ a:ueous layer to another container. 0e careful to lea6e the organic layer in the round/botto$ flas!. #ransfer the organic layer and re$aining a:ueous layer into a 3 $L conical 6ial. .llow the two layers to se-arate and re$o6e the botto$ a:ueous layer with a -i-et. .dd ' $L of water to the 6ial9 gently sha!e the 6ial9 and then re$o6e the botto$ a:ueous layer. 12tract the organic layer with '/4 $L of saturated sodiu$ bicarbonate

36 solution and then re$o6e the botto$ a:ueous layer. #hese ste-s ser6e to -urify the organic -roducts of lefto6er acid9 alcohol9 salts etc. .dd granular anhydrous sodiu$ sulfate to the organic layer to dry the -roducts and ca- the 6ial with a #eflon ca- until you are ready to analyze the -roducts by +,R and G%. =uestions9 ='> On the +,R s-ectru$9 label the !ey -ea!s you were loo!ing at and e2-lain their relati6e che$ical shifts. In other words9 why is one shifted further downfield than the other. )or the gas chro$atogra-h9 which co$-ound has a longer retention ti$e and whyE =*on;t ?ust say it has a higher boiling -oint//e2-lain why>. =4> 7hat were the ratios of '/bro$obutane('/chlorobutane for the +,R and G%E 7hich results do you thin! are $ore reliable if there was a differenceE =3> 0ased on your results9 which nucleo-hile is better( 0r/ or %l/E 12-lain the theory behind nucleo-hile strength and state which nucleo-hile should be better. =4> 7hat are the li$itations of gas chro$atogra-hyE *escribe a situation where it would not wor! well. =3> 7hat are the li$itations of +,RE *escribe a situation where it would not wor! well. =6> 12a$ine the results fro$ the e2-eri$ent with 4/$ethyl/4/-ro-anol. 7hat !ind of a reaction was itE 12-lain your answer.

38

Dehy)ration of Cyclohe*anol
OH

H.

H2O

7ac%groun) Read --. 648/3' for a discussion of reagents and the $echanis$ of alcohol dehydration. @ou will wor! in -artners in this e2-eri$ent. One -artner will carry out the reaction 6ia the traditional $ethod9 using a $i2ture of -hos-horic and sulfuric acids as a catalyst. #he other -artner will carry out the reaction using a cation e2change resin as the catalyst.

,icroscale Reflu2 .--aratus 1roce)ure <reheat a sand bath to a te$-erature of a--ro2i$ately '"5/455 o% while the reaction a--aratus is being set u-. <lace 4.5 g of cyclohe2anol in a 3 $L conical 6ial. +irst ,artner( .dd 5.43 $L of 83D &3<O4 and 4 dro-s of &4SO4 to the reaction $i2ture. Second ,artner( .dd 5.45 g of the ion e2change resin =.$berlyst '3> to the reaction $i2ture. .dd a s-in 6ane or boiling stone and a &ic!$an distillation head fitted with a water cooled condenser. Gradually heat the $i2ture until the -roduct begins to distil. Regulate heating so that the distillation ta!es 35/43 $inutes. .s crude -roduct distils fro$ the reaction $i2ture9 use a -i-et to transfer distillate fro$ the &ic!$an still head to a closed 6ial. 7hen the distillation is finished9 rinse the inside of the still head with ' $L of saturated +a%l solution and add this solution to the -roduct $i2ture. Re$o6e the lower a:ueous layer9 then carefully decant the organic layer into a dry test tube and add ca. 5.4 g of anhydrous +a4SO4. 7hile the -roduct is drying9 clean and dry the &ic!$an head and s-in 6ane. Reasse$ble the a--aratus with a ther$o$eter sus-ended through the condenser into the botto$ of the still head. <i-et the clear organic li:uid into a dry 3 $L conical 6ial and add a boiling stone or s-in 6ane. *istill the -roduct9 collecting the fraction that boils between 84 and 83 o%. .nalyze your -roduct by obtaining IR and +,R s-ectra of it. 0e sure to weigh your distilled -roduct and calculate a -ercent yield. %o$-are the -roduct obtained using the traditional acid catalyst to that fro$ the ion e2change resin. =uestions
'

,oeur9 &. <.C Swati!9 S. ..C <innell9 R. <. J !hem Ed. !!89 #49 833.

38 ='> 0ased on your IR and +,R s-ectra9 did the reaction yield the correct -roductE 0e s-ecific in citing e6idence fro$ your s-ectra. =4> 7hat was the -ercent yield for each $ethodE &ow could you i$-ro6e the -ercent yieldsE =3> 7hich dehydration $ethod see$ed to wor! betterE 12-lain your answer.

3"

+)entification of an -n%no,n
In this e2-eri$ent you will be gi6en an un!nown organic co$-ound and you will use a series of che$ical and s-ectrosco-ic tests to deter$ine its identity. @ou will only need to fill out the following for$ during labC there is no -relab or re-ort due. #he -ossible $ain functional grou-s include( aldehydes9 a$ines9 carbo2ylic acids9 !etones9 and alcohols. Other functional grou-s $ay also be -resent. #he structures and na$es of the -ossible un!nowns will be -osted in the laboratory. @ou will obtain a s$all 6ial of the un!nown and should then carry out the following tests9 although the order in which you carry out these tests is not i$-ortant. ='> %lassify the li:uid by color and s$ell. =4> <erfor$ che$ical tests described below. 7rite the che$ical reactions for any -ositi6e tests. =3> Obtain an IR s-ectru$ and analyze it9 labeling any -ertinent stretches for functional grou-s on the s-ectru$. =4> Obtain an +,R s-ectru$ and analyze it. Identify functional grou-s based on che$ical shifts and al!yl grou-s based on integration and s-litting. =3> <ro-ose a structure. @ou will be allowed to lea6e when you get it correct. 3cetyl Chlori)e 'est .lcohols react with acetyl chloride9 gi6ing off heat.
O Cl O

. $OH

O$

. HCl

%autiously add about '5/'3 dro-s of acetyl chloride9 dro- by dro-9 to about 5.3 $L of the li:uid un!nown in a s$all test tube. 16olution of heat and &%l gas indicate a -ositi6e test. Lucas 'est <lace 4 $L of Lucas reagent in a s$all test tube and add three to four dro-s of the alcohol. Sto--er the test tube and sha!e it 6igorously. #ertiary9 benzylic9 and allylic alcohols gi6e an i$$ediate cloudiness as the insoluble al!yl halide se-arates fro$ the a:ueous solution. .fter a short ti$e9 the i$$iscible al!yl halide will for$ a se-arate layer. Secondary alcohols -roduce cloudiness after two to fi6e $inutes. So$e secondary alcohols $ay ha6e to be heated slightly to $a!e the reaction -roceed. <ri$ary alcohols dissol6e in the reagent to gi6e a clear solution. R/O& N &%l
/nCl2

R/%l N &4O

D51 'est .ldehydes and !etones =but not esters> react with 494/dinitro-henylhydrazine =*+<> to gi6e an orange or red -reci-itate9 which indicates a -ositi6e test.
$
O 0H1$

H2N

H N

NO2

H.
NO2

0H1$

H N

NO2

NO2

<lace one dro- of the li:uid un!nown in a s$all test tube and add ' $L of the 494/*+< reagent. Sha!e the $i2ture 6igorously. ,ost aldehydes and !etones will gi6e a yellow to red -reci-itate

45 i$$ediately9 but so$e co$-ounds will re:uire u- to '3 $inutes =or gentle heating> to gi6e a -reci-itate. Note( ,any *+< deri6ati6es are sus-ected carcinogens and should be handled with care. Chromic 3ci) 'est .lcohols =-ri$ary and secondary> and aldehydes react with chro$ic acid =Bones reagent> to gi6e a blue/green -reci-itate in this test. .ldehydes are o2idized to carbo2ylic acids. Secondary alcohols are o2idized to !etones9 and -ri$ary alcohols are o2idized first to aldehydes and then to carbo2ylic acids. Getones and tertiary alcohols are unreacti6e under the test conditions.
3
OH 3
O

.
H

2 H2C O4 . 3 H22O4
3

3
OH O

. C 202O413 . 3 H2O

. 2 H2C O4 . 3 H22O4

. C 202O413 . 5 H2O

*issol6e one dro- of a li:uid un!nown in ' $L of acetone. .dd se6eral dro-s of the chro$ic acid reagent a dro- at a ti$e9 while sha!ing the $i2ture. . green -reci-itate and loss of the orange color of the reagent indicate a -ositi6e test. #he -reci-itate $ay for$ within 35 seconds or it $ay ta!e a few $inutes. If a -reci-itate for$s and the solution re$ains orange9 the test is negati6e. Note( ,any co$-ounds of chro$iu$ are sus-ected carcinogens and should be handled with care.

4'

-n%no,n 0eport (heet

n!nown +u$ber %olorIS$ell Solubility Tests

+a$e

<ossible )unctional Grou-=s>

Chemical Tests 7rite out che$ical reactions for any -ositi6e tests.

<ossible )unctional Grou-=s> IR .nalysis =.ttach labeled s-ectru$.> +,R .nalysis =.ttach labeled s-ectru$> Proposed Structure

44

3ppen)i*
sol6ent acetic acid acetoneV dichloro$ethane =$ethylene chloride> diethyl etherV =ether> ethanolV ethyl acetateV he2aneV $ethanolV -etroleu$ etherV 4/-ro-anolV =iso-ro-anol> water %&3%&O&%&3 &4O 1hysical 1roperties of (ol2ents for$ula density =gI$L> %&3%O4& %&3%O%&3 %&4%l4 %&3%&4O%&4%&3 %&3%&4O& %&3%O4%&4%&3 %&3%&4%&4%&4%&4%&3 %&3O& '.53 5.8" '.34 5.8' 5.85 5."5 5.66 5.8" 5.63 5.8" '.55 boiling -oint =o%> ''8 36 45 33 88 88 6" 63 35/65 84 '55 '8.3 88 dielectric constant => 6.'3 45.85 ".58 4.333 44.33 6.54 '.8" 34.8

V#hese sol6ents are fla$$able.