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    14 views17 pages

    Manual Solucoes26 PDF

    Uploaded by

    Douglas Sampaio

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    © All Rights Reserved
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    of 17
    Chapter 26747 Solutions to Problems a. Stearic acid has the higher melting point because it has two more methylene groups (giving it a greater surface area) than palmitic acid. b. Palmitic acid has the higher melting point because it does not have any carbon-carbon double bonds, whereas palmitoleic acid has a cis double bond that prevents the molecules from packing closely together. . Oleic acid has the higher melting point because it has one double bond, while linoleic acid has two double bonds, which give greater interference to close packing of the molecules. CH,CH,CH,CH,CH,CH=CHCH,CH=CHCH,CH=CHCH,CH=CHCH,CH,CH,COOH | L.excess O; 2. HyO, i it ‘ i CH;CH,CH;CH,CH,COH 3 HOCCILCOH HOCCH,CH,CH,COH hexanoic acid 3 malonic acids glutaric acid 3. All tiacylglycerols do not have the same number of chirality centers. If the carboxylic acid ‘components at C-1 and C-3 of glycerol are not identical, the triacylglycerol has one chirality center (C-2). If the carboxylic acid components at C-1 and C-3 of glycerol are identical, the triacylglycerol has no chirality centers. 4. Glyceryl tripalmitate has a higher melting point because the carboxylic acid components are saturated and can, therefore, pack more closely together than the unsaturated carboxylic acid components of glyceryl tripalmitoleate, is = Coo! = = COOH en OL 748 Chapter 26 6. Because the interior of a membrane is nonpolar and the surface of a membrane is polar, integral proteins will have a higher percentage of nonpolar amino acids. 7. The bacteria could synthesize phosphoucylglycerols with more saturated fatty acids because these triacylglycerols would pack more tightly in the lipid bilayer and, therefore, would have higher melting points and be less fluid. 8. The sphingomyelins can differ in the fatty acid component of the amide and have either choline or ethanolamine attached to the phosphate group. a. CH=CH(CH;),2CH3 CH=CH(CH)),,CH3 CH—OH i 9 CH-OH 9 CH-NH—C(CHp))2CH3, CH-NH—C(CH;),4CH: g ea Qo ge CH, —O—P—OCH,CH:NCH CH, —O—F—OCH,CH,NCH3 oO CH; o- CH; CH=CH(CH,)2CH3 CH-OH 9 GHONH~C(CH,)4CHs iy CHy—O—P—-OCH,CH,NH & be CH=CH(CH,)1.CH; CH-OH i CH-NH—C(CH,),4CH, H HOH 20H Oi “ 0 on 9. Membranes must be kept in a semifluid state in order to allow transport across them. Cells closer to the hoof of an animal are going to be in a colder average environment than cells closer to the body. Therefore, the cells closer to the hoof have a higher degree of unsaturation to give them a lower melting point so the membranes will not solidify at the colder temperature. Chapter26 749 10, = ‘COOH OH PGC, 11. 12, The fact that the tail-to-tail linkage occurs in the exact center of the molecule indicates that the two halves are synthesized (in a head-to-tail fashion) and then joined together in a tail-to- tail linkage. CO tail-to-tail linkage 750 Chapter 26 13. Squalene, lycopene, and B-carotene are all synthesized in the same way. In each case, two halves are synthesized (in a head-to-tail fashion) and then joined together in a tail-to-tail linkage. 14. Solved in the text. 15. first step of 9° o oO the Claisen i > ji onde tion CHCCH,CSCoA + CO, - CH,CSCoA z NS SSCA | second step of the Claisen condensation Se 1) CHjCCH,CSCoA + CoASH agl g [2s C—CH,CSCoA | Sadition tt 1,0. Vd CHsGCH,CSCoA + CoASH — CHSGCHCSCoA + CO, CH,CO™ CHGSCOA Chapter26 751 16, 9 9 AALS a3 P. 0 IN INoe S INNS 790-9 oo oo E isomer rotate about single bond YB S e @? AY LH ° HB’ + Pp < to ol Oo N/ No oN AN. wee | 0 9-0 Zisomer tenes 17. Ss —- T0y —> e) ‘OPP; geranyl 1 OH + H,O* pyrophosphate ceterpineo! S — + #0" J ‘OPP; CH: SS geranyl qu Pyrophosphate H limonene 752 18, 19. 20. 21. 22. Chapter 26 + H,0° Solved in the text. ‘A pehydrogen at C-5 means that the A and B rings are eis fused, whereas an a-hydrogen at C-5 means that the A and B rings are trans fused. Because the OH substituent is on the same side of the steroid ring system as the angular methyl groups, itis a #-substituent. ‘The hemiacetal is formed by reaction of the primary alcohol with the aldehyde. Chapter 26753 24, Because the three OH substituents of cholic acid are on the opposite side of the steroid ring system as the angular methyl groups, they are all a-substituents, Two of the OH substituents are axial substituents and one is an equatorial substituent. 754 Chapter 26 25. There are two hydride shifts and two methyl shifts. The last step is elimination of a proton. HC. CH; CH, protosterol cation | 2snyide HAC, CH3 HC. CH; CH, + CH; CH. CH, 26. If stearic acid were at C-1 and C-3, the fat would not be optically active. ‘Therefore, stearic acid must be at C-1 and C-2 (or C-2 and C-3). 9 CH,-O—C—(CH))gCH3 cH—0-€ (CH) CH CHy-O—CCH,)4CH3 27. 29, Chapter 26755 a, There are three triacylglycerols in which one of the fatty acid components is lauric acid and two are myristic acid, Myristic acid can be at C-1 and C-3 of glycerol, in which case the triacylglycerol does not have any chirality centers. If myristic acid is at C-1 and C-2 of glycerol, C-2 is an asymmetric carbon, and consequently, two enantiomers are possible for the compound. There are six triacylglycerols in which one of the fatty acid components is lauric acid, one is myristic acid, and one is palmitic acid. The three possible arrangements are shown below (with the fatty acid components abbreviated as L, M, and P). Since each has an asymmetric carbon, each can exist as a pair of enantiomers for a total of six triacylglycerols. CH)-O=L CH)-O—L CH;-O—M *CH—O-M +CH—O—P +CH—O-L CH)-O—P CH,-O—M CH)-O—P a I RICO” R3CO™ CH,-OH e 7 3 CH—OH R?CO” — RACO™ "| CH)—O—C—CH. pore ts CH—O—-C—CH, 5 7 CH, —O—C—CH CH)-OH ‘The structure at left has a molecular formula = CoH 40, and a molecular weight = 218. Subtracting 218 from the total molecular weight gives the molecular weight of the methylene (CH,) groups in the triacylglycerol 722-218 = 504 Dividing 504 by the molecular weight of a methylene ‘group (14) will give the number of methylene groups. 504 14 Since there are 36 methylene groups, each fatty acid in the triacylglycerol has 12 methylene groups. = 36 756 Chapter 26 9 " CH —O—C—CH,CH,CH,CH,CH,CH,CH,CH,CH,CH,CH,CH,CHs " GH—0—C—CH,CH,CH,CH,CH,CH,CH,CH,CH,CH,CH,CH,CH, " CH, —O—C—CH,CH,CH,CH,CH,CH,CH,CH,CH;CH,CH,CH,CH,, nutmeg 30. Chapter 26-757 31. a. Starting with mevalonyl pyrophosphate, you can trace the location of the label in the compounds that lead to the formation of geranyl pyrophosphate, and geranyl pyrophosphate is converted to citronellal. OH Lu 1 CH,CCH,CH,OPP, ~——> —CH,CCH,CH,OPP, I 1 “ 4 cHCo” cH, CH,C=CHCH,OPP, 4 isopentenyl pyrophosphate but, mevalonyl pyrophosphate dimethylallyl pyrophosphate \ S ee $e uL x0 oy = CH,C=CHCH,CH,C=CHCH,OPP, | 1 ‘OPP, geranyl pyrophosphate citronellal b. The label is lost from sample B when mevalonic pyrophosphate loses CO2 to form isopentenyl pyrophosphate, so none of the carbons will be labeled in citronellal. OH cuyecngcH,0PR > cHccH,cH,oPR, + Go, CH;CO™ CH j S 758 Chapter 26 ¢. Because the methyl groups are equivalent in the carbocation that is formed as an intermediate when isopentenyl pyrophosphate is converted to dimethylallyl pyrophosphate, either of the methyl groups can be labeled in dimethylallyl pyrophosphate. This means that either of the two methyl groups can be labeled in gerany! pyrophosphate and in citronellal. ou + CH,CCH,CH,OPP; ——> CH,CCH,CH,OPP; FE cc cucu,orri veH Co HCH, Guth G isopenteny! pyrophosphate irs mevalonyl pyrophosphate | M4 CH;C=CHCH,OPP| + CHyC=CHCH,OPP; CH, MCHs yt dimethylallyl pyrophosphate 14 ve fae ee (CH,C=CHCH,CH,C=CHCH,OPP; + CHyC=CHCH,CH,;C=CHCH,OPP; geranyl pyrophosphate | uy Ss up c=0 c=0 H | H “ Chapter 26-759 32. There are five possible structures for compound A, and two possible structures for compound B. HAC. CH a we 4S cH, + HO HC CH, BC. CHa CH OH B B CH; CHy HAIPd ‘Hy/Pd a Ae H,/Pd nf fase Nw jC. (CH; HC. CH; OH OH NG Noh HC. LCHy HCLCH HCL LACH, OH OH CH. CH; CH, CH; CH A A A A 760 Chapter 26 33, Because acetyl-CoA is converted into malonyl-CoA (see Section 26.8), mevalony pyrophosphate will contain three labeled carbons, which means that juniper oil will contain six labeled carbons. OH u ah wt CHsCSCoA ——™ “OCCH,CSCoA ——> CH, (CHCH,OPF, MCH EO oO mevalonyl pyrophosphate | “is ad CHJE=CHCH,OPR, —<—— —CHCCH,CH,OPR 14CH3 14CH), dimethylallyl pyrophosphate isopentenyl pyrophosphate / 4 14 4 14 ua Te ug Te ao WS CHj;C=CHCH;CH,C=CHCH,OPP, = — geranyl pyrophosphate 3) ‘OPP, m if 14 14 Onl4 geranyl pyrophosphate juniper oil 34. Chapter 26 761 762 Chapter 26 b. Ithhas 30 carbons, so it is a triterpene. 35. CH: CH: + HO 36. ‘The OH groups will react only if they are in equatorial positions, because introduction of bulky axial substituents would decrease the stability of the molecule. In the case of Sa-cholestane-38,76-diol, the two OH groups are on the same side of the ring system as the angular methyl group, which means that they are in equatorial positions. Both OH ‘groups react with ethyl chloroformate. Chapter26 763 In the case of Sa-cholestane-3,7<-diol, only one of the OH groups is on the same side of the ring system as the angular methyl group. The other is on the opposite side of the ring, which ‘means that it is in an axial position. Only the OH group that is in the equatorial position reacts with ethyl chloroformate. jal - CH, equatorial c~ cH; oH H He A axial H H H on__/ Sa-cholestane-36,76-diol Sa-cholestane-38,7a-

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