Laman

Sabtu, 07 Juli 2012

jawaban soal ujian


1.       fats generally are solid while the oil is liquid phase , however both are equally triglyceride . explain why the form of two different triglyceride , and point out important factors that determaine the form of fat ?
answer :
 because fats is saturated than oil is unsaturated. There are many different kinds of fats, but each is a variation on the same chemical structure. All fats are derivatives of fatty acids and glycerol. The molecules are called triglycerides, which are triesters of glycerol (an ester being the molecule formed from the reaction of the carboxylic acid and an organic alcohol). As a simple visual illustration, if the kinks and angles of these chains were straightened out, the molecule would have the shape of a capital letter E. The fatty acids would each be a horizontal line; the glycerol "backbone" would be the vertical line that joins the horizontal lines. Fats therefore have "ester" bonds. The properties of any specific fat molecule depend on the particular fatty acids that constitute it. Different fatty acids are composed of different numbers of carbon and hydrogen atoms. The carbon atoms, each bonded to two neighboring carbon atoms, form a zigzagging chain; the more carbon atoms there are in any fatty acid, the longer its chain will be. Fatty acids with long chains are more susceptible to intermolecular forces of attraction (in this case, van der Waals forces), raising its melting point. Long chains also yield more energy per molecule when metabolized.

 A fat's constituent fatty acids may also differ in the C/H ratio. When all three fatty acids have the formula CnH(2n 1)CO2H, the resulting fat is called "saturated". Values of n usually range from 13 to 17. Each carbon atom in the chain is saturated with hydrogen, meaning they are bonded to as many hydrogens as possible. Unsaturated fats are derived from fatty acids with the formula CnH(2n-1)CO2H. These fatty acids contain double bonds within carbon chain. This results in an "unsaturated" fatty acid. More specifically, it would be a monounsaturated fatty acid. Polyunsaturated fatty acids would be fatty acids with more than one double bond; they have the formula, CnH(2n-3)CO2H and CnH(2n-5)CO2H. Unsaturated fats can be converted to saturated ones by the process of hydrogenation. This technology underpinned the development of margerine.
Saturated and unsaturated fats differ in their energy content and melting point. Since unsaturated fats contain fewer carbon-hydrogen bonds than saturated fats with the same number of carbon atoms, unsaturated fats will yield slightly less energy during metabolism than saturated fats with the same number of carbon atoms. Saturated fats can stack themselves in a closely packed arrangement, so they can freeze easily and are typically solid at room temperature. For example, animal fats tallow and lard are high in saturated fatty acid content and are solids. Olive and linseed oils on the other hand are highly unsaturated and are oily.
Saturated fatty acids have higher melting points than unsaturated fatty acids,Saturated fatty acids adopt a fully extended conformation, pack well, and have strong van der Waals attractions between molecules.
Cis double bonds in unsaturated fatty acids put bends in the chainUnsaturated fatty acid chains pack poorly and have weaker van der Waals attractions between molecules than saturated fatty acids Unsaturated fatty acids have lower melting points than saturated fatty acids with the same number of carbons
Triacylglycerols with a higher content of saturated fatty acids have higher melting points,Triacylglycerols in animal fats contain mostly saturated fatty acids and are solids are room temperature,Triacylglycerols in oils have a large proportion of unsaturated and polyunsaturated fatty acids and are therefore liquids are room temperature.

2.       how a primary metabolite can be converted into secondary metabolites . what is the basic idea and how the mechanism could be described ?
answer :
the basic ide is  The building blocks for secondary metabolites are derived from primary  metabolism. The number of building blocks needed is surprisingly few. The most important building blocks employed in the biosynthesis of secondary metabolites are derived from:
  1. Acetyl coenzyme A (acetyl-CoA)
  2. Shikimic acid
  3. Mevalonic acid
  4. 1-deoxyxylulose 5-phosphate
  5. Amino acids

3.      BIOSYNTHESIS PROGESTERONE
progesterone  like all other steroid hormones, is synthesized from pregnenolone , which in turn is derived from cholesterol. This is  step reactions to formation progesterone 
  •  Cholesterol  undergoes double oxidation to produce 20,22-dihydroxycholesterol.
  •  This vicinal diol is then further oxidized with loss of the side chain starting at position C-22 to produce pregnenolone. This reaction is catalyzed by cytochrome P450scc.
  •  The conversion of pregnenolone to progesterone takes place in two steps. 
    • First, the 3-hydroxyl group is oxidized to a keto group  
    •  second, the double bond is moved to C-4, from C-5 through a keto/enol tautomerization reaction. This reaction is catalyzed by 3beta-hydroxysteroid dehydrogenase/delta(5)-delta(4)isomerase.
 

Progesterone in turn  is the precursor of the mineralocorticoid aldosterone, and after conversion to 17-hydroxyprogesterone (another natural progestogen) of cortisol and androstenedione. Androstenedione can be converted totestosteroneestrone and estradiol.

4.Alkaloid Synthesis: (S)-Nicotine (Helmchen), (+)-CP-99,994 (Shi), (-)-Adaline (Yu), (-)-Securinine (Bayón/Figueredo), Alkaloid 223A (Aubé), (-)-Huperzine A (Fukuyama)

The recent development of practical methods for the asymmetric preparation of amines has enabled creative approaches to alkaloid construction. Günter Helmchen of the Ruprecht-Karls-Universität Heidelberg developed (Synlett 2009, 1413. DOI: 10.1055/s-0029-1217165) an iridium catalyst that mediated the enantioselective amination of the allylic carbonate 1 to give 2. Hydroformylation followed by reduction then completed the synthesis of (S)-nicotine (3).
Yian Shi of Colorado State University devised (J. Org. Chem. 2009, 74, 7577. DOI: 10.1021/jo9015584) a Pd catalyst for the enantioselective oxidative diamination of terminal alkenes such as 4. The product 6 was readily carried on to (+)-CP-99,994, a potent and selective nonpeptide substance P receptor antagonist.
Chan-Mo Yu of Sungkyunkwan University prepared (Synlett 2009, 1498. DOI: 10.1055/s-0029-1217172) the alcohol corresponding to the azide 8 by BINOL-catalyzed addition of an allyl stannane to the corresponding aldehyde. Reduction of the azide and subsequent intramolecular condensation with the ketone gave an imine, that was cyclized with Bu3SnF to 9. Oxidative cleavage then delivered (-)-Adaline (10).
Barry M. Trost of Stanford University developed a family of Pd catalysts for the enantioselective coupling of racemic butadiene monoepoxide 12 with a range of nucleophiles. Pau Bayón and Marta Figueredo of the Universitat Autónoma de Barcelona extended (J. Org. Chem. 2009, 74, 6199. DOI: 10.1021/jo901059n) that range to include glutarimide 11 and succinimide. The adduct 13 provided the enantiomerically-pure core for a total synthesis of (-)-Securinine (14), and others of the Securinega alkaloids.
Jeffrey Aubé of the University of Kansas prepared (Org. Lett. 2009, 11, 4140. DOI: 10.1021/ol901645j) the enantiomerically-enriched ketone 15 by the enantioselective hydroboration of norbornadiene, followed by oxidation and alkylation. Intramolecular Schmidt cyclization following the protocol he had developed converted 15 into 16. He then took advantage of the still-substantial ring strain of the expanded norbornene to drive ring-opening metathesis, to give, after hydrogenation, the lactam 17. He was able to selectively convert 17 into either 18 or the diastereomer in which the ethyl groups are cis one to another, by varying the acid used in the final reductive work-up.
To prepare the bridged bicyclic core of (-)-Huperzine A (22), Tohru Fukuyama of the University of Tokyo began (Org. Lett. 2009, 11, 5354. DOI: 10.1021/ol9022408) with the monoester 19, readily prepared from the furan/maleic anhydride Diels-Alder adduct by the known quinine-mediated opening with benzyl alcohol. The aminated quaternary center of 22 was established by inversion of the carboxy group of 21.
.


 
 


4.