University of Balamand Faculty of Sciences Basic Organic Chemistry CHEM 240 Exercises Dr.Rima KassabExercises: 1. Give the IUPAC name: ay AA nae 2. Write the structural formula of: a) 3- ethyloctane bb) ay a b) 4 Isobutyl - 1, 1 - dimethyleyclohexane ©) Cyclomethyl eyclopentane 3, Determine whether the 2 structures are: 1) Constitutional isomers 2) Conformations 3) Sterioisomers oo ay) 4 u mA ag WOH cH chy 4 H H He b) > 8s eq, Ye ee we A v1 4S and WAC 4 hs cH? a w aa ® wa chs Gin BPRS we > a Cc Dsage fc cS€ Draw the Newman projections (looking down the c-1-c-2 bond) for the most stable conformation of 2, 2-dimethylpropane aes > Haya B---4 : y yee — SN " B-H4 Sox’ “t \ ‘ — 7 i c x vy NYS “Transition state A different mechanism: The E1 mechanism CH Ach OL COWs), © CHCH, DEON, CAS C CH,CH,+ CCHy),C = CHO 1 Ry heat one cK Mechanism: ve Stow HO 4 CHattle CW, CCHLCH, ——> Cc + Br $a ' Be uy we BEE ste NaS CHa ee Has hi aoe co 3 Alkyne nomenclature Monosubstituted alkynes: RC =CH + Terminal A\ Keyne Disubstituted alkynes: RC =cR' + interval eet aePreparation of alkynes by elimination: + Double dehydro hategenation ofa germinal kchalide Matsa CCH 3), C CH cuct, Te? CHa), Coe CHAlkenes and Alkynes 1 xer’ 1. Give the structures of 2 different alkyl bromides both of which yield the indicated alkene as the exclusive product of E2 elimination = c) ct, a) Cyt = CHa << a 6b) Cette), C = CHa 2. What 3 alkenes may be formed from the acid-catalyzed dehydration of 2-pentanol? Which one will predominate? CHCCHa) a, CHOHS) 2 oY on es cu AY von Which one reacts faster by E2? 4. Give the structures of the organic product of each of the following reactions a *« CH. US0q Ow Heat ») Ay HCl OK ow” eet warn ©) Product of Co) + Na ack, —+Alkenes and Alkynes 2 Exercises: 1. Write the structures of the major organic product or products formed on treatment of I-pentene with each of the following: a) HCL ») HBr ©) Dilute Sulfuric acid 4) Bromine ©) Bromine in H20 2. Give the structure of the principal organic product formed on reaction of 2,3-dimethyl-1,3-butadiene with each of the following: a) AL CEO) ) PE dA wot KCI CProduct of 4 2 aakd) c)L mot HCL CProckuct oP 1,4 add) Dimot Bra CPraductof 1,1 add) Dimol Bra CProctuctof LAH add) D2 mor Be 3. Write the structure of the major product isolated from the reaction of I-hexyne with: a) Ha Camot), ee Ds Cl mot) 5 Lindtar’s cok OMA WHS ANMAWH 2/7 HL 2) Product of Cat) with 4-lbromolutane D ACL Clmoll act C2 mol) HaS0y caqy » MASCQ 4. Suggest a sequence of reactions for preparing the following compounds: a) 2-methylhexane from 2-methyl-2-hexanol 'b) 2-propanol from 1-propanol c) 1,2-dibromopropane from 2-bromopropane pas a) cay es COD, Yo Dy weet CG Sea aL Ney Wok os ope ay okey CH (o-4y) SF, Nam Re Blow @Aromatic Exercises: ° L._ Name the following compounds: . cu cHCCHa) ) eo ON ») OL ~) s e a cusch > ee e) Chatty 76. Gh Poy CG QA Cia ar 2. When benzene is treated with propene and sulfuric acid, 2 different monoalkylation products are possible. Draw their structures. Which one do you expect to be the major product? Why? 3. Indicate the main monosubstitution products in each of the following reactions: ANWORENZENE + Coccentralld sulfuric acidCineat) + SO 3 by AAUENE + Bromine Ce catalyst) Atoluene + acery\cnlorcle CAICla, catalyst) 4. Predict whether the following substitutions on the benzene ring are likely to be ortho, para-directing or meta-directing and whether they are likely to be ring-activating or ring-deactivating; ? ° a ¢-ocbs BNH-CEHs C)SCH, A) Hy CCHade 5. Using benzene or toluene as the only aromatic starting materials, devise a synthesis for each of the following, 8) p-chloronitrobenzene b) prnitroethylbenzene ¢) m-chloronitrobenzene 4) 2-bromo-4-nitrotoluene Cc o oom qe Pee OD as ee 8 8 ot ersh au oe)Stereochemistry Exercises: 1. Locate with an asterisk the chiral centers a) CHA) CH 3, b (ae > CHa CHD 2, Tell whether the following structures are identical or enestiomers: cl a . \ ay Ltn and aa cus CH aC Oo, TH CK 3. Tell whether the stereogenic centers marked with an asterisk inthe following structures have the R or the S configuration: a yg cag ay AA by ALN aaa e NO cH LON al cuca). “2 e Ow fe — Cc Ww > CHINN CH a, AS Wo4, Which of the following fisher projection formulas have the same configuration as A? Che « E ox @& Ge And which are its enertiomers? of 4 Coy ayeh—|— Gis rats} — chs oo. ° a ou on 5. Convert the sawhorse formula below for one isomer of tartaric acid toa fisher projection formula. Which isomer of tartaric acid is it? cat ot HO cuSubstitution and Elimination Exercises: 1. Tell what product you expect, and by what mechanis reactions: it is formed, for each of the following a) |-chloro-I-methyl cyclohexane + ethanol }) I-chloro-I-methyl cyclohexane + sodium ethoxide (in ethanol) Answer: Cis o YN <> + CHACH,OH + el ia SNL e cha 7 YC MM + CH ACH, Otay ——> ca ey 2. Explain the different products of the following reactions: CH=CH CUCM ge cu, we —p CH=CH CH - CH ev C208 CH, =CH-CU Clty + ClCH ——P CH= CH— CH —cHs + CHE cuCH, ‘ : ®y Oct, OcHs 3. Combine an electrophilic addition and a nucleophitic substitution to devise a 2-step synthesis of: Ct ce, CH, ay Clts CM CHL CH fom Ct ocH3 CH chs 1 —c— \ by CHC CH cas hom Cuy- C= CCHS OCsCo = oN 4, Devise a synthesis of: AY CHZOCH Hs Bom On atkoxide and AN AKL Moe od CHZOCCCH s)3 Mom an alconol andan alkyd Wobide 5. Combine a nucleophilic substitution with a catalytic hydrogenation to synthesize: AY CUsCH.CHLOH Rom CHi= CHCH. Br © Cés-r-pentine Som propyrte and loromoeHwont-Alcohols, Phenols, and Thiols Exercis 1. Name each of the following compounds: a on @) 4 co _ ©) 6 By C Ze 2 ox ow oI A 4 Lr e) CHa cl CHa 2. Show the structures of all possible acid-catalyzed dehydration products of the following: ) Cyclopentanol b) I-methyleyclopentanol ©) 2-butanol 4) 2-phenylethanol Write an equation for each of the following 2-step-synthesis: © Cyclohexene to cyclo hexainone v) 4- chlerobutan, > butanol cy) 1- butannt fo t- butanetniol 4. Write an equation for each of the following reactions: @ 2- metyy) - 2- bulanol + HCI Yo) t- Pentanol + Na ©) Cacto pentanol + PReg ay 2-Phenylethrancl & oct, @ - ) 4- methylcyctepentanot LL 1) 4 pentanol + CrOs, AT 4) D-eyclomexs| EMranol + PCC.Ethers and Epoxids Exercise 1. Name each of the following compounds: (CH, CHE CH CCHS), (CBR CH CHS OCH cu — cu a) Ar —L~- c) ae oe ) Or-VYy OCH, oO F) CHg0cHichi csc e) Cees 3 a 2, Write equations for the best method to prepare each of the following ethers: a FS b) CH CHOC CCH a) a Ne O -CHACHCH 3, 3. When heated with excess HBr, a cyclic ether gave 1,5-dibromopentene as the only organic product. Write a structure for the ether and an equation for the reaction Answer = CHa - CHa - CHa — CHL - OF 1 or > Be eC \7 4. Using the peroxyacid epoxidation of an alkene and the ring opening of an epoxide, devise a 2-step-synthesis of 1,2-butanediol from I-butene Anguoer > A pi = CH. -CH - CH, CH CH=CH Ce oa an » \ ok OF5. Design a synthesis of 3-pentyn-1-ol of using propyine and ethylene oxide as the only sources of carbon atoms Cus -¢ * ce, CHL / _ Anawey? CHyC= CH + Nad, GREE | CMa CM Sy G Bt / 0 CC ec- CHi 7 CHa 6 Not Cue SC—-CHHLO ——— ~Aldehydes and Ketones Exercises: 1. Name the following compounds: 8 O) Ch ychs E cucu s by CHHs), C=O ©) (CHa, CHAO DOr g-aa LW ° a e) Br Cus Ces fy cugcu CHE CHa 3 2. Write an equation for the synthesis of 2-pentanone by: 4) oxidation of an alcohol b) hydration of an Alkyne 3. Write an equation for the reaction, if any, of bromobenzaldehyde with each of the following reagents: . ay Cros,4* ay eee gyeh# % CHAN e) NH De OD tn 4) clay CHa - Ma. Br, 4307 4) Lo ALH gy 4. Complete each of the following equations: a) buG@nol + excess methanol, yt b) CHa ctiCOChs), + Wio, wt + Hiro, Ht ec) 4 \e Oo Cy aby CO excess CltacHs ott, ut XQ or5. Using a Grignard reagent, and the appropriate aldehyde or ketone, show how each of the following can be prepared: a) L-pentanol b) 2-methyl-2-pentanol ) I-phenyl-1-propanol 4) 3-butene-2-ol 6. Complete the equation for the reaction of: 2 a) f Wt /H20 1G 4+ NaC? Ct —_- ° KOK b) oy a Hon > _ c) 1- butanene + VHT OH ——> 7. Give the structure of each product: ° ! CAL a Chg l- ZH TOUS N= * eds b) 7S ct = Ch ~cuso 2XCess Ha = ——— Ney wea \r ces Q | ON BEY oO DUD, Ut O Gy cuctreso Sons . 7 oo, i FeagqatCarboxylic acids and its derivatives Exercis 1. Give equations for the synthesis of: @) Clack, ck ,CO. 4 Rom CH ACH, CHCA OW wd Cusack chi COg 4 Bem CH, CH, CH. OM oc = CL“ CBB om cl — ED SBP 8 Open hem e) CHSOCHC0,# From Cha — CHa 7 No 2. Write a structure for each of the following compounds: a) sodium-2-chlorobutanoate ») phenyl benzoate c) ethyl formate d) benzonitrift 3. Write and equation for the reaction of ethyl benzoate with: @ aynmontov Io) watthyl maqneacurn Codede Crep), then Wot CY Leto aluminem hydds Gee), tren Haot 4. Identify the Grignard reagent and the ester that would be used to prepare: ow Gs \ ‘ oO ct —c —CHACH3 \ ClCH, ; b) Clactsch ~ ¢ - or as Cus5. Complete the equation for each of the following reactions: B® Chach OW, uy 4 PUg b CH a ) OX + KM ROG eS CH >, c) oo ce CONH, + Le AL Gy —e NCS rane, 2 Alga cal A 18% GC) oT Gal 7 Ws Ved ae 1) Ahi COs mi