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    Exercises Carbonyl Condensation Reactions

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    Exercises Carbonyl Condensation Reactions

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    Carbonyl Condensation Reaction

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    Carbonyl Condensation Reaction

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    Exercises Carbonyl Condensation Reactions

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    Carbonyl Condensation Reaction

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    Problems 941 [8] Dieckmann reaction (24.7) ost 2. With 1,6-diesters: [ILNaOEL 0 BHO oct et e, . With 1,7-cesters: 0 [1 Naoet ‘OE aH,o" bet PROBLEMS — The Aldol Reaction 24.27 Draw the product formed from an aldol reaction with the given starting materials) using “OH, H,0. (CH),CHCHO only 9 (CH),CHCHO + cH, (C.HyCHO + CH,CH,CH,CHO t + cycHo 124.28 What four f-hydroxy aldehydes are formed by a crossed aldol reaction of CH,CH,CH,CHO and C,H,CH,CHO? 124.29. Draw the product formed in each directed aldol reaction, ma 2 rmuon cusooH, ICCCRGHS oncus ost) ine [3]H,0, 430 bree poco when eth dato campoind vege ral il main lowed by dyn CHO rT g ° 24.31 What starting materials re needed to synthesize each compound using an aldol or similar reaction? a CoH HON 24.82 A published synthesis ofthe analgesic nabumetone uses a crossed aldol reaction to form X. What isthe structure of X? X 's converted to nabumetone in one step by hydrogenation with H, and Pe-C. (See Problem 23.28 for another way to make rnabumetone,) CHO (Hs0=0 th NaOET Pac cH,0 10H cro abumetone ° 942, Chapter 24 Carbonyl Condensation Reactions 24.83. What dicarbonyl compound is needed to prepare each compound by an intramolecular aldol reaction? ° = Oo CO +4 24.34 Identiy the structures of C and D in the folowing reaction sequence. 1) los NaoH I eg MOH og BCH IS Ho CigHeo The Claisen and Dieckmann Reactions 24.35. Draw the Claigen product formed from each ester a. G(HiCH,CH,CH,CO,Et ©. cHo—{ )cHcooet b. (CH),CHCH,CH,CH,C0,et 24.26 What four compounds ate formed from the crossed Claisen reaction of CH,CH,CH,CH,CO,Et and CH,CH,CO,Et? 24.37 Draw the product formed fram a Cisisen reaction with the given starting materials using “OEt, EtOH, CHCH,CH,CO,ER only ° CH,CH,CH,CO, Et 44,00, A CH,CH,CH,CO,Et + (CH),0=0 0 (OP + Heoget E{O;CC(CHy},CH,CH,CH,CO,Et OiHsCOCH,CH, + CyH:CO,Et CH,CH,CO,Et + (EtO),C=0 24.88 What starting materials are needed to synthesize each compound by a crossed Clalsen reaction? ° oH,0. ' i . BAT e AA Sete « caontcooens Cost 88 7 24.38. The 1-sketone shown below can be prepared by two diferent Caisen reactions —ramely, one thal forms bond (a) and one that forms bond (). What starting materials are needed foreach of these reactions? 2 0° bona (—' bohd (oh 24.40. Even though B contains three ester groups, a single Dieckmann product results when Bis treated with NaOCH, in CH,OH, followed by Hj0". Draw the structure and explain why its the only product formed. a ° ° co So, 8 Problems 943 Michael Reaction 24.41. Draw the product formed fram a Michael reaction withthe given starting materials using “OEt, E1OH, ° ° ° a Ae 4 om Tc F] + crite, . a ee yo 124.42 What stating materials are needed to prepare each compound using a Michael reaction? _— ° ° ° 8 a eA. A Che Co,et —c0,et “ ° cut, co,et 24.43. f-Vetivone is isolated from vetver, a perennial grass that yields a vaiety of compounds used in traditional eastern medicine, pest contal, and fragrance, In one synthesis, ketone A is converted to f-vetivone by a two-step process: Michael resction, followed by intramolecular aldo reaction. (a) What Michael acceptors needed for the conjugate addition? (See Problem 23.68 for another method to orm the bicyclic ring system of f-vetvone) (b) Draw a stepwise mechanism forthe aldal reaction, which forms the six-membered ring \ ° , +e aye OO ge Ory a OO Robinson Annulation 24.44 Draw the product of each Robinson annulation from the given starting materials using “OH in H,0 solution ° 944 Chapter 24 Carbonyl Condensation Reactions Reactions 24.46. Draw the organic products formed when butanal (CH,CH,CH,CHO) is treated with each reagent "0H, HO 1 NaBH,, CHOH k. CFOs, 4,80, b.-OH, CH,=0, H,0 g. Hs, Pd 1. Bre, CHCOCH [1] LDA: [2] CH,CHO; [3] H,0. h. HOCH, CH,OH, TsO rm. PhyP=CH, 4. CH,(CO,EN,, NaOEY, EtOH CCHNH,, mild acie 1. NaCN, HCl @. [1] CHLE 2) HO (CHY,NH, mild acia ©. [N]LDA; [2] CHE 24.87 Draw the organic products formed in each reaction ° ° a “oH id InLoa. 70) cH PICHACHRCHO a1H.0 ° ° aoe £0 com . eraie=o ‘Cr . chor ° g Cw ae 9 rociyco,e: MOR HON “y+ i O= AS cn Ow ch,00,€ 4 ~ In] Na0et, 10H cco * cus! Boy, ee "GG BIH," 24.48 Fillin the lettered reagents needed for each reaction. da dere de & + faek : bththhe de Gro 24.49. Explain why vinyl halides such as CH,=CHCI undergo elimination by an EtcB mechanism more realy than alkyl halides such {as CHyCH,C a 24.50 Identity lettered intermediates A-D In the folowing reaction sequence. \ yr Mos ro HOH [1] Naoet, EtOH Te, eee > Bers 180, H;S0, Ko" #0. Cysts Problems 945, 24.51 Identity compounds A and B, two eynthetlc intermediates in the 1979 synthesis of the plant growth hormone gibberellic acid by Corey and Smitn. Gibberelic acid induces cel division and elongation, thus making plants tall and leaves large. g4 OD [oy NaOH several siens x CHS oH CsHesOe rot COLH gbberellc ac Mechanisms 24.52. When acetaldehyde (CH,CHO) is treated with three equivalents of formaldehyde (CH, =O) in the presence of aqueaus Na,CO,, (HOCH,,CCHO is formed as product, Draw a stepwise mecharism for this process, 24,53. In theory, the intramolecular aldol reaction of 6-oxoheptanal could yield the three compounds shown. It tums out, though, that ‘-acotylcyclopentene is by far the major product. Why are the other two compounds formed in only minor amounts? Draw a stepwise mechanism to show how all tree products are formed, cho a ° AL Ss D { \ Ago te + +f \ CHO F,0 OX oe LD S-oxoheptanal ‘-aceiyleyelopentene major product 24.54 Draw a stepuise mechanism for each cyclization reaction. ° (a1HO" cHso0e YY [1] Naocts 6 VAL BRS doch, 24.55 Draw a stepuise mechanism forthe folowing variation of the aldel reaction, often called a nitro aldol reaction. as, + ce 24.56 Draw a stepuise mechanism forthe following Robinson annulation. This reaction was a key step ina synthesis ofthe steroid cortisone by R. B, Woodwatd and co-workers at Harvard Universit in 1951 Q ps ~ Nao ] oS ieveal cortisone 946 Chapter 24 Carbonyl Condensation Reactions 24.87 Green polymer synthesis—the preparation of polymers by environmentally riencly methods using stating materials that are not derived from petroleum —is an active area of research. One example isthe polymerization of tulpalin A, anatural product darived trom tulips, to afford polytulpalin. Polytulipalin has properties similar to some petroleur-derived polymers, but its availabilty from a natural source has made ita possible attractive alternative to these polymers. Polymerization occurs in the presence of a strong base (B), and each new C~C bond in polytulipalnis formed by a Michael reaction. Draw a stepwise ‘mechanism for the formation of one C—C bond in polytulipain. (See Section 20.8 for other aspects of geen polymer chemistry) eee WA on a aeteaee {w-mothylonerrbutyrolactone) 124.58 Coumarin, a naturally occurring compound isolated from lavender, sweet clover, and tonka bean, is made inthe laboratory from co-hydroxyberzaldehyce by the reaction depicted below. Draw a stepwise mechanism for this reaction. Coumarin dervatives are useful synthetic anticoagulants, 2 chcoo- Nat on, + CHCOOH + HO ‘Ch o-hydroxybenzaldenyde coumarin 24.59 (a) Draw a stepwise mechanism for the reaction of yexadienoate with diethyl oxalate in the presence of base. b) How {does your mechanism explain why a new carbon-carbon bond forms on C8? (¢) Why is this reaction an example ofa crossed (Claisen reaction? ° AAR + (609th BE poe AP + CH Synthesis 24.60 Convert acetophenone (CyHsCOCH,) into ‘other organic compounds or required inorganic reagents 1ch Compound. In some cases, more than one step is required. You may use any co-cd OO 24.62. Synthesize each compound from cyclohexanone and any other organic compounds or required inorganic reagents. More than ‘one step may be needed. ° ° ° ° Ann 2k bk Ai ARN -O "OO FOL HOR + OD Ww Problems 947 24,83 Devise a synthesis of each compound from cyclopentanone, benzene, and organic alcohols having <8 C's. You may also use ‘any requires organic or inorganic reagents. ° cr dg 1 8S Or om 24.84 Devise a synthesis of each compound ftom CH,CH,CH,CO,E%, benzene, and alcohols having <2 C's, You may also use any required organic or inorganic reagents. ee ee 24.65 Devise a synthesis of each compound from cyclohexene. You may also use any required reagents. ° A » Opa 8 a et ade 24.66 Octinoxate Is an uneaturated ester used a an active ingredient in sunscreens. (a) What carbonyl compounds ate needed to synthesize this compound using a condensation reaction? (0) Devise a synthesis of octinoxate from the given organic starting materials and any other needed reagents. Ss — jf + aleohols with <5 c's Ho 9 oe CH,0" 4 General Problems 24.87 Four steps in the synthesis of helminthosporal, a toxin produced by & wheat plant fungus, are shown below i ie Lge i OO te 8) | Na0et, EtOH \What compounds are needed to cany out Step 2]? ° v4 A et + HoOE 4 Write a detailed mechanism for Step [3] Write a detailed mechanism for Step [4]. What's unusual about the product ofthis reaction? Step [1] adde 2 formyl group (HCO) and Step [3] removes it. Why was this apparently unnecessary process done? SSS. LA hetminthospora ‘What compounds are needed to cary out Step [1]? 948 Chapter 24 Carbonyl Condensation Reactions Challenge Problems 24.88, Propose a stepwise mechanism forthe flowing resction ofa fketo eter. Suggest a reason why his rearangement reaction occu. q {1] NaOCH,CH,, i 0.0K 0H cHycH.OH cO.cHCHy PHO" 24.69 Ieophorone is formed from three molecules of acetone [ICH On the presence of base, Draw a mechanism for ths process ° isophorone 24.70 Draw a stepwise mechanism for the folowing reaction. [Mint: Two Michael reactions are needed] inl svong base ( Ro ~7>co,0H, 24.71. 4-Metnylpyridine reacts with benzaldehyde (C

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