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    Dienoss

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    Machetin Machetin

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    Solutions to Exercises for CHAPTER 1 0 ADDITION REACTIONS OF CONJUGATED DIENES 10.1. Follow the procedures outlined in the solutions to the nomenclature exercises in Chapter 1 a, (2Z,4Z)-4-Methyl-2,4-heptadiene hept seven carbon atoms 2d-diene two double bonds, starting at C2 and C4 4-methyl CEh group at C4 Zz the higher priority groups at the ends of the bond are on the same side of the C=C bond az the higher priority groups at the ends of the bond are on the same side of the C=C bond b, 2-Fluoro-1-penten-3-yne pent five carbon atoms Len double bond starting at C1 3eyne triple bond starting at C3 2-fluoro F atom at C2, © 2-Chloro-1,3-cyclohexadiene cyclohexa ring with 6 carbon atoms ch d. (QE, 4Z)-2,4-Hexadienal hea 6 carbon atoms 2-cliene two double bonds, starting at C2 and C4 °CHy 4 al aldehyde group; its carbon atom defines C1 y 7 Ho 2 the higher priority groups atthe ends ofthe Se Eng bond are on opposite sides ofthe C=C bond Lod az the higher priority groups atthe ends ofthe bond are on the same side of the C=C bond reise LIZ. 102. Follow the procedures outlined in the solutions to 2 This compound has the carboxylic acid functional group at the end of the carbon chain, so the name ends in *-oic acid.” The longest carbon chain that includes both the carboxylic acid carbon atom and the double bonds has seven carbon atoms, so the root is hept. There are two carbon-carbon double bonds, so the multiple bond index is diene: hept/diene/oic acid = heptadienoic acid. Numbering begins with the carboxylic acid carbon atom. 5E)-3-methyl-2,5-heptadienoic acid. 158 ORGANIC CHEMISTRY SOLUTIONS MANUAL 402. (continued) b. This compound has a ring of six carbon atoms with one double bond within the ring: cyclohexene, The other carbon-carbon, double bond is external to the ring, so it is named as a substituent, isopropylidene (Section 8.1c). The substituent specifies the assignment of C1 for the ring, so the name is isopropylidene-2- cyclohexene, ©. This compound has both a double and a triple bond. Numbering can begin at either end of the chain, but the numbers would be the same (I-buten-3-yne versus 3-butene-L-yne), so we choose the first because a double bond has the higher priority. “Ene” is placed in. 1 the name before “yne” in either case. A phenyl group is attached to Cl and a chlorine atom is attached to C2. The configuration of, the double bond is (Z), so the compound's name is (Z)-2-chloro- phenylbutene-3-yne. 4. This compound has a seven-membered ring and three carbon 2 carbon double bonds, starting at C1, C3, and C3. A tert-butyl : group is attached at Cl, so the name is I-tert-butyl13,5- 3 cycloheptatriene. 103. Isolated double bor ridized carbon atom (a. and di). Cumulated double bonds (c). The ends of conjugated double bonds are separated by a single carbon-carbon bond (shown in color in part b.). ey = sp? hybrcizaion C= sphybridzaion on curlat HOW isolated G04. Bonding molecular orbials are formed by the mathematical addition of the combining orbitals” aaa o¢-<: filled with two electrons Antibonding molecular orbitals are formed by the subtraction of one orbital from another, which means that changes occur in the mathematical signs of the orbital being subtracted. The highest electron density lies away from the region between the atoms. The node of each hybrid orbital at the nucleus is retained in this combination, and a new node is created in the space between the atoms. CHAPTER 10/ ADDITION REACTIONS OF CONJUGATED DIENES 159 705. The energy of a bonding molecular orbital (MO) is lower than the energy of the hybrid orbitals undergoing combination. The energy of the antibonding MQ is higher than the energies of the combining hybrid orbitals. Because each hybrid orbital contributes one electron to the MOs, there are two electrons and they are used to fill the bonding MO (a). The high energy antibonding MO (o*) is empty. 10.6. The reaction of a conjugated diene with chlorine will produce both 1,2- and 1,4-dichloro products, Ifa new chiral center is produced, then both configurations will be generated at the chiral carbon atom. For the 1,4-addition process, it is necessary to consider the formation of double bond isomers, which result fom rotation about the sigma bond. It is worthwhile to draw the structures of the possible carbocation intermediates. This diene is symmetrical, so it does not matter which double bond we start with, (4 H aH cr 107. Follow the procedure outlined in the solution to Exercise 108 The elecirophile & HF and the nucleophiles water (OH). Both alcohol products ate achiral chy “ H,0, H2SO4 460 ORGANIC CHEMISTRY SOLUTIONS MANUAL 10.8. Follow the procedures outlined in Example 10.3 a. Generate the possible carbocations (and their resonance forms) by protonating each double bond separately, and then decide which set of cations is more stable. NOT tm adr An CHy HH CHy HH HH Ant ae An —_ AY Tis set otcatocaion omy ‘The products are formed by attaching the bromide ion to the carbocation centers in the more stable set. The kinetic product is derived from reaction with the more stable carbocation of the pair, and the thermodynamic product is the one with the more highly substituted double bond, 2 _ er CH CH Hye ‘br CHy Br Kinetic product Thermodynamic product (rlgubsttuted doube boas) b. Generate the possible carbocations (and their resonance forms), and then decide which set is more stable. This diene is symmetrical, so only one set of carbocations is formed. co cO- 00 ‘The products are formed by attaching the bromide ion to the two carbocation centers, The kinetic product is derived from reaction with the more stable carbocation, and the thermodynamic product is the one with the more highly substituted double bond. Co- co cb. | Kinetic product H br ‘Thermodynamic product (etrasubsttvied double bord) Generate the possible carbocations (and their resonance forms), and then decide which set is more stable, ‘This set of carbocations is more stable Ot DoD ‘> = "Ds nd CHAPTER 10/ ADDITION REACTIONS OF CONJUGATED DIENES 161 408. (continued) ee inate penn BY attaching the bromide ion to the carbocation centers of the mote stable ae netic Product is derived from reaction with the more stable carbocation cones wee thermodynamic product isthe one with the more highly substituted double bona 3 2 Br. + Br er CHy ‘CH; + CHy ‘cH Kinetic product Thermodynamic product (trisubstituted double bond) 10.9. The product of the Diels-Alder reaction lv. a cyclohexene derivative in which the substituents have ee ——— GSE ——r—————e a caat aaa nt ext 0 each other, and then connect the ends of their m systems foo ree ee ”—i—Cs—ss—s—t—s—Csr—_—O Fro in tas eee Pol atthe bond between the double bonds inthe starting diene. For the reas thoes) a ake ew chiral centers are produced from achiral starting compounds (ieee by the asterisk), so each transformation yields a racemic mixture, TE — Oot Ae A Tolow the procduae ound in Brwsie 10 For the lant own WN WOR oe Crete a produced from achiral starting, compounds finicted by the seinen oe transformation yields a racemic mintore 3 The diene in this reaction is not symmetrical, so the reactants have to be oriented so that the ester Stoup ofthe dienophile is directly below (or above) the diene x system, os shone below at the right, This orientation yields the relative stereochemistry shown, cs oct, HOCH a cooch, coocH, H c fo ie. (CHy8i0- SES (ons (cH4,80 TO ‘eceme E=CcoocH; b. The diene in this reaction is symmetrical but itis cyclic, so the reactants have to be oriented so that {he cyano group ofthe dienophileis directly below (or above) the iene e system, as shown below at the right. This orientation yields the relative stereochemistry sheen ol — as, _ 162 ORGANIC CHEMISTRY SOLUTIONS MANUAL, JoA1. All of these reactions yield products in which the elements of H and Cl have added to one of the double bonds. When there are no substituents attached to the ring of a cyclic diene (conjugated or isolated), then the product appears as if only one of the double bonds has reacted. In other words, the 1,2- and 1,4-addition products are identical for the conjugated dienes. A new chiral center is generated from achiral reactants, so a racemic mixture is produced in each case, oT OF H a Ho a © H Oo Ce a_i Oe : 10.12. Follow the procedures outlined in Exercises 10.9 and 10.10. ® a P— AL» AY 10.16. Given the structure of a cyclohexane derivative that has been formed via the Diels-Alder reaction, you need only break the two bonds in the six-membered ring that are connected to the carbon atoms adjacent to the double bond (shown as colored clots in the following structures). ‘These carbon atoms define the termini of the diene system, and the other two carbon atoms define the double bond (or triple bond, in part c,) of the dienophile. . Cr 7 Cur CH we "= 2. f.. CHO ‘ay Oo re co lghacd ‘covet Hyco~ Se gooes G +t ¢ Covet 464 ORGANIC CHEMISTRY SOLUTIONS MANUAL 07, The middle carbon atom of the cumulated diene double bonds has sp hybridization, as do the two alkyne carbon atoms of the cyclic alkyne product. The bond angles of a carbon atom with sp hybridization are 180°, so the diene product should be less strained within a 10-membered ring because only one carbon atom has this geometric constraint imposed upon it. Hence the cumulene is formed in greater quantity than the alkyne, os < al < CO em Lo © (60% ied) on PP Ratio; 3:2 FOIE To solve THs ype of problem, Hast wate out the synthesis scheme as a ow diagram. The ast reaction, to form compound D, is clearly a Diels-Alder reaction, so we follow the procedure given inthe solution to Exercise 10.16 to deduce the structure of the diene, which is compound C. Oey 20 bin CrCl Na0cH{(CHa Sr aos ee ether solvent, 3 o ‘A diene can be formed by treating a dibromoalkane with strong base, which corresponds to the reaction conditions that are given. A dibromoalkane can be prepared by adding bromine to an alkene, so we identify the compounds as follows O= DD = O=— Mh cyclohexene )49. Follow the proc a. Generate the possible carbocations (and their resonance forms), and then decide which set is more stable _ ' AS an Sine be The products are formed by attaching an OH group to the carbocations of the more stable set. The CH kinetic product is derived from the reaction with the more stable carbocation, and the thermodynamic product is the one with the more highly substituted double bond. Kinetic product or (substituted doubte bond) CHAPTER 10 / ADDITION REACTIONS OF CONJUGATED DIENES 165 joa9. (continued) Generate the possible carbocations (and their resonance forms), and then decide which set is more stable. This diene is symmetrical, so only one set of carbocations is formed, The products are formed by attaching the methoxy group to the carbocation centers. The carbocations ate equivalent and the double bond substitution pattern of the products is the same (disubstituted), so there is no clear choice for the identities of the thermodynamic and kinetic products. We would therefore expect to obtain equal amounts of each product no matter what the reaction conditions are. c= 0 Oe S86 OCH Both intexmediates are 2° carbocations. Both products have a disubsttuted double bond 0.20. For stable alkenes and polyenes with » number of p orbitals, there are MOs, 1/2 of which are bonding orbitals and filled; and 1/2 of which are antibonding orbitals and vacant. The lowest energy MO has no node and (1 ~ 1) overlapping pairs. With increasing energy, an additional node is added between atoms (vertical dashed lines) and the numbers of pairs of overlapping orbitals decreases by one, At the highest energy MO, the number of nodes reaches its maximum, and there is no pair of overlapping orbitals. The bonding MOs have more overlapping, pairs of orbitals than nodes, and the antibonding, ‘MOs have more nodes than overlapping pairs. There are six electrons to add to the orbitals, and these fill the bonding MOs. NODES OVERLAPPING PAIRS Yet, —— 5 o ¥8 —— 4 1 — 3 2 ENERGY 186 ORGANIC CHEMISTRY SOLUTIONS MANUAL 10.21. This cycloaddition reaction takes place in the same manner that a typical Diels-Alder reaction does. The nitrogen atoms in the product have sp? hybridization, so they are planar and it is not necessary to consider whether the product has an endo or exo orientation (it is neither), _-COOEt w a i + N—COOEt onl / N, covet 10.22. For a delocalized system with x number of p orbitals, there are n MOs. For allylic systems, there are three MOs, The lowest energy MO has no node, the next highest MO has one node, and the highest energy MO has two nodes. Notice that the node in ris at C2; an MO with a node at an atom position is, classified as non-bonding. In filling these orbitals, we start with the lowest energy MO and add electrons. For the allyl carbocation, only ‘is filled. The allyl radical has a single electron in 2 and the allyl carbanion has both and filled. Noves 2 yy — vy a 1 ‘ % » 4 I tl | », ° Hp Cr al “Ff Hoc=cH—EH, = HC=CH—CH, © HyC=CH—CH ‘The resonance forms make use of i and Ys, which are either bonding or non-bonding orbitals, ‘The antibonding MO is not involved. 1033. To predict reagents involved. products formed inthe addition reactions of dienes, begin by assessing the ypes of + Is the reagent electrophilic (H-, Cl, Br) or neutral (Diels-Alder reaction)? + If the process starts with a reaction between a diene and an electrophile, de the reaction conditions suggest kinetic or thermodynamic control? + Ifa Diels-Alder reaction is taking place, what is the stereochemistry of the reactants? For reactions that generate a diene, make use of what you learned about elimination reactions in Chapter 8 a. In this transformation, a diene reacts with a proton in the first step. The low temperature (© 0 °C) is most likely meant to indicate that kinetic solutions to Exercise 10.8 to deduce the structures of the kinetic and thermodynamic products. Both products have a new chiral center, so both are racemic. ntrol is desired. Use the procedures illustrated in the CHAPTER 10/ ADDITION REACTIONS OF CONJUGATED DIENES 167 ion ary 70.23. (continued) O- m & . a ‘Thermodynamic product Kinetic product b, In this transformation, a diene reacts with an alkene having clectron-withdrawing substituents, so this s 2 Diels-Alder reaction. Use the procedutes outlined in the solutions to Fxereees inn and 10.10 to deduce the structure of the product. This product has two new chiral center as vot as a mirror a i plane of symmetry, soit is a meso compound. e 5 CoS aoe i CN \ “SCN In this transformation, a diene reacts with an alkene having an electron-withdrawing substituent, so this i a Diels-Alder reaction. Use the procedures outlined inthe solutions to Exercises 10.9 and 10.10 to deduce the structure ofthe product, which will be endo. The produict has three vey chiral centers 80 itis obtained as a racemic mixture. a-r— Ae. a 4 In this transformation, an alkyl halide reacts with a strong base, so an E2 mechanism is likely. The slimination must occur away from the bridgehead atom hecause » double bond to the bridgehead atom would be too strained, The product is achiral, KOH, ethanol Product of) achiral a Oe -r—~—“—™C—C—COSC—COCOCOCOCN (greater than room er ———_——— “ ® the rom gee iustated in the solution to Exercise 108 to deduce the stractues ofthe tinge and iRewmodynamic products, The thermodynamic product has 4 new chisd wnten it would be ee and both are achiral Ww ee CR ~ + \ 50°C racemic achiral achiral Thermodynamic Kinetic product Kinetic product Product Major 468 ORGANIC CHEMISTRY SOLUTIONS MANUAL 10.23. (continued) f. In this transformation, chlorine adds to the alkene double bond to form a vicinal dichloride. The strong base in step 2 is used to promote E2 reactions, which generate the conjugated diene, Within a ring having fewer than nine atoms, a triple bond or cumulated double bonds cannot be formed. The product is achiral, Ne CHC TD Kom ehanok a 024, If the mechanism for L4-addition were to occur by the route shown in part (a), you would expect to isolate only the cis isomer. The actual mechanism, shown in (b.), will yield both cis and trans products because the intermediate carbocation is free to undergo rotation about the C2-C3 bond when the carbocation is localized on C2. (The 1,2-addition products are not shown.) ar = OQ Sf cis on LIG y VV ly or er er er Br oom |e ~€ , ol: atound the

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