Fundamentals of Organic Chemistry I
Fundamentals of Organic Chemistry I CHEM 202
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Date Created: 11/01/15
CHEMISTRY 34 Enolates and Condensation Reactions Protons on saturated carbon next to carbonyl groups are slightly acidic because the anions are stabilized by resonance o 09 H eOH 3 e an enolate R C CHZ R39 R c CH R39 4 R CCH R39 These anions nucleophiles can add to other molecules of the same carbonyl compounds at the electrophilic carbon ofthe carbonyl mechanism also reproduced on earlier handout C 0 II I o O OH I I ll 9 I R C CH2R II I H2O R C CH RH R CCH R gt R C CIDH CID CHZR39 gtR C CIH CI CH2R39 R39 R R39 R When the carbonyl compounds are aldehydes or ketones the reaction is known as the aldol condensation Some examples I 3 I CH3 C H2 CH gtOH CH3 C H2 C H C H CH catalyst IH 3 O 0 OH H NaebCH3 II I C CHs gt C CHZ CI In CH30H CH3 0 O NaeeocHZCHs M gt in CHsCHZOH OH Sometimes the two carbonyl compounds can be different though not often There are extensive rules as to what works and what doesn t This reaction has an important biological equivalent in the metabolism of glucose CI3H20P03H2 CI3H20P03H2 CI3H20P03H2 ltIO 90 9 ltIO HOCH HOCH HOCH2 Dihydroxyacetone phosphate gt e H ch OH and H C OH H CI30 HZOPOsHZ HCOH DGlyceraldehyde3phosphate Fructose 16 diphosphate CHZOPO3H2 A Reverse Aldol Condensation as Drawn see over The same kind of reaction takes place with esters which also have acidic C H s This process is known as the Claisen condensation 0 9 0 0 II Na OCHZCH3 II II R CHZ C OCHZCHs gt R CHZC CH C OCHZCHs In CHgCHZOH I This reaction requires a whole equivalent of base because the product is more acidic than the reactant and is deprotonated to a highly resonance stabilized anion gtNa H2 H3 R H H 4 R CHz ICC OCH CH lt gt RCH amp CIC OCH CH in CHSCHZOH CHz C I C OCH2CH3 I 2 3 2 I 2 3 R can be recovered from this anion by adding H3O Note that the best base in this process is the alkoxide with the same structure as the ester alcohol which thus avoids several kinds of side reactions including transesteri cation and hydrolysis M h 39 O 09 II ec anIsm D 90R 6 H I RCH2COR R CHZC OR39W R CH C OR39lt gt R CHc 0R39 gt O O I II 90R39 II II R CHZCIE CIEH C OR39 gt R CHZ C CIEH C OR39 OR39R R same as above Claisen Condensations are critical in two major biosynthetic pathways 0 CHs C Acetyl CoA an ester with S in place ofthe O the group becomes a better leaving group than a simple alkoxide as above 6 359 CHZC SCOA lt gt owe sow lAcetyl CoA I l 9 l CH3C CH2C SCoA CH3C CH2C SCoA gt to MevalonicAcid Acetyl CoA I CHz i SCOA O reduce ketone repeat and repeat Fatty Acids Squalene terpenes Vitamins A E K steroids isopentenyl pyrophosphate CHEM 34 f and Uses of Some lmnnrtanf f 39 quot Acids Formic acid from Latin formica sant IUPAC methanoic acid Up to 10 of body weight of 3 some kinds of ants is formic acid a corrosive irritating liquid partly responsible for sensation caused H c OH by ant and bee stings Isolated by distillation of ants Commercially however it s usually made by oxidation of formaldehyde H Acetic acid IUPAC ethanoic acid Vinegar is a ca 5 solution of acetic acid Acetic acid CH3 C OH equivalents are key builiding block in metabolism of living cells Progionic acid IUPAC propanoic acid An antifungal agent often used in athlete s foot salves CH CH ampOH The sodium and calcium salts eg calcium propionate are food additives frequently added to 3 2 bread to inhibit mold formation The fatty acids The glyceride esters of these acids are fats lipids The most common include CHg CH214 002H Palmitic acid Almost all long chain acids found In livrng cells whether or not they contain one or more CC CH3 CHZM 002H w bonds have an even number of carbon atoms Wh 2 You ll find out in Biochemist CHa CH27 CHCH CH27 002H Oleic acid y W OH Lactic acid Found in milk cheese sauerkraut Small amounts found in human blood and cells I 0 generated by breakdown of carbohydrates Muscle cramps during exercise are caused by presence CH3 CH Clt of high concentrations of lactic acid in muscle tissue The high concentration is due to lack of sufficient oxygen to oxidize and thus get rid of this acid from muscle Commercially lactic acid is added to many food products to make them more acidic eg olives cheese soft drinks 0 Fluvic acid Key intermediate in sugar metabolism In muscle pyruvic acid is reduced to lactic CH gc o acid during exertion Not easy to isolate because it decomposes on standing 3 OH Oxalic acid Occurs as the water insoluble calcium salt in spinach rhubarb etc Kidney stones in O O H H people are usually calcium oxalate Large amounts of oxalic acid are toxrc Up to 50 ofthe dry HO C C OH weight of certain leaves is oxalic acid Such plants are harmful to animals Rhubarb is boiled before being eaten to decompose the oxalate Oxalate is the product of metabolism of many molds eg penicillium Oxalic acid is used in industry as a bleaching agent radiator cleaner and spot remover Potassium oxalate is used in clinical laboratories to prevent blood coagulation blood Ca2 precipitates as the oxalate and none is left in solution to promote coagulation O Citric acid A tricarboxylic acid One of the most widely distributed plant acids H H citrus fruits Commercially made by fermentation using a specific bacterium Used in HO C CHfC CHfC OH soft drinks sherbet and many other foods to provide flavor Also a blood anticoagulant because it complexes Ca2 Also acts as a buffer eg in Alka Seltzer OCOH and other effervescing powders dissolve 3 Nazcos 2 H3CeH5O7 W 3 H2003 2 Na3CeH5O7 base citric acid solution white solid white solid of Na citrate decomposes to HzO 002 gas the bubbles in Alka Seltzer l 9 9 l HO C CH CH C OH OH 9 O I OH ll 0 CH2 ICH CH2 ICH xCH2 ICH OC O C O IC OH OH OH OH 9 OH Tartaric acid In foods effervescent powders as above The mono potassium salt is used in baking powders as the acid to cause formation of 002 bubbles same principle as above from the carbonate formed by bacteria or chemically during heating This is how the so called air bubble spaces in cakes and breads are created Tartaric acid is also used as a laxative Benzoic acid The Na salt sodium benzoate is a common food preservative especially in soft drinks catsup pickles pie fillings jams margarine The salt is odorless tasteless nontoxic and an effective bacteriacide at conc of 01 Also used for this purpose in cosmetics NOTE the average American consumes 3 lbs of food additives for preservation flavor color etc per year Salicylic acid This is a better disinfectant than phenol It s used in many topical ointments The top layer of skin flakes off the underlying skin is unharmed used to remove corns and other horny tissue 18501890 PreAspirin also Na salt Acetzlsaliczclic acid Aspirin Introduced in 1899 used to relieve pain analgesic as an antiinflammatory arthritis rheumatic conditions to reduce fever antipyretic and uric acid reducer gout treatment a uricosuric In US g 100 5 grain tablets used per person per year 40 tons a day in US Mechanism of action still partly unknown 7A acetic acid 240 245Trichloroghenoxzacetic acid 235T Plant hormones Used in excessive amounts they overstimulate the plant and kill it Were used as defoliants in Vietnam aNagthzlacetic acid Used to reduce premature dropping of apples Polyacg lic acid Remember polymerization of acrylic acid CH2CH COZH Polymer used in preparation of ion free water Used in diets of heart patients to control concentration of Na ion The ion exchanger used in water softening t systems exchange between Na salt and Ca2 Fee and Mg2 sal s Cholic acid One ofthe principal acids in bile Derivatives of these are used to solubilize fats emulsify to permit passage through intestinal wall and assimilation Note relationship to cholesterol from which it is made in the cell CHEM 34 Important Representative Esters Methyl Formate IUPAC methyl methanoate A fumigant for tobacco Ethyl Acetate A major industrial solvent Ethyl Propionate IUPAC ethyl propanoate Artificial peach flavor nPentyl Propionate Apricot essence A Low molecular weiqht many have sweet or fruitv smells H C O CH3 CH3C O CH2CH3 CH3CH2C O CH2CH3 CH3CH2C O CH2CH2CH2CH2CH3 0 CH3 3Methylbutyl Acetate Banana oil CH3C O CH2CH2CH CH3 0 CH3 C H22C O C H2 C H3 CH3 C H25 C O C H2 C H3 f C O C H3 f C O C H2 C H3 f QC O C H3 NH2 f H2 C H3 OH o CH3 Ethyl Butyrate Used in the manufacture of artificial rum Its solution in alcohol is known as pineapple oil Ethyl Heptanoate Also called ethyl oenanthate cognac oil oil of grapes artificial cognac essence AlphaMethylene Butyrolactone This is a lactone or a cyclic ester the alcohol and acid portions are in the same molecule Oil of dogtooth violets Methyl Benzoate Used in perfumery as Peau d Espagne Ethyl Benzoate Also used in perfumery odor similar to the methyl ester above Called Essence de Niobe Methyl 2Aminobenzoate Methyl Anthranilate Artificial neroli oil Principal constituent of ylangylang oil Ethyl 4Aminobenzoate Benzocaine Used as a surface topical anesthetic Methyl Salicylate Oil of Wintergreen Flavoring agent for candies and used in perfumery Also used as a inament note relationship to salicylic acid and aspirin O C CH3 2Acetylsalicylic AcidI Aspirin Most widely used painkiller OH O B Polymeric Monomer Name Vinyl Polymer 0 Vinyl Acetate Polyvinyl Acetate adhesives CH3C O CHCH2 l Meth l Ac late Acr lic lastics aints CH2CH C O CH3 y W V P P l f CH2CCOCH3 Methyl Methaorylate Polymethyl Methacrylate Lucite or PleXIglass CH3 Also Condensation Polymers O 9 9 THZO ll 9 9 9 HO CHz CHzOH HO C C OH gtvva CH2CH2 O C O CHTCHZ 0 CW n This is Dacron o o o 0 H20 II II II HO CHz C OH gt WO CHZ C O CH2 C O CH2 CW n This is Dexon a polymer used as the thread of surgical stitches which are absorbed and biodegraded by the patient s body C Lipid Type Animal Fat Triesters of glycerol with long chain saturated acids Triglycerides Soaps made by boiling with aqueous NaOH saponification hydrolysis Vegetable Oil Triesters of glycerol Triglycerides with long chain acids containing several CC bonds Remember softness of a fat is a function of number of double bonds Remember preparation of margarine by hydrogenation O OH A monoglyceride Some of these are commercial products eg with R as H C17H35 stearate or C15H31 palmitate used as moistening agents in cake R C O C H2C H C H2OH mixes Waxes For example Beeswax Carnuba Wax Spermaceti Wax from head of sperm whale used to make candles These are esters of long straight chain fatty acids Cw030 with long straight chain alcohols 020040 Both the acid and the alcohol components contain an even number of carbons CHEMISTRY 202 IMPORTANT OVERHEADS ALKANE STRUCTURE VS PROPERTY RELATIONSHIPS INTERNAL COMBUSTION ENGINE r PISTON V BURNING x CHAMBER VIA AI k I J I39SPARK AIR amp GAS INTAKES XY COMPRESSION RATIO OCTANE NUMBER IS AN EMPIRICAL MEASURE OF THE MAXIMUM COMPRESSION RATIO AT WHICH A GASOLINE BLEND WILL BURN SMOOTHLY OCTANE 73 IS MAXXY 51 91 81 98 101 PETROLEUM REFINING TO OBTAIN GASOLINE Purpose To maximize the amount of branched alkanes in the C5 to C10 range Use Three Processes 1 Convert mixture of larger alkanes higher boiling fraction to smaller molecules done by heating at high temperature with catalysts cracking 2 Connect smaller molecules together lower boiling fraction to get bigger molecules done with catalysts at low temperature called alkylation buildup 3 Convert alkanes of the same size molecular weight to more branched isomers done with acid catalysts at low temperature reforming ALKANE SERIES COMPOUND BP MP QM PENTANE 36 C 130 C 063 HEXANE 69 95 068 HEPTANE 98 91 070 OCTANE 126 57 072 NONANE 151 54 073 DECANE 175 30 074 METHANE BP 162 C MP 183 C DENSITY 042 900 M COMPOUND EB CH3 CH2 C HQ CI IzCI Iz CH3 69 C CH3 l 63 C CH3CH2CH CH2 CH3 CH3 I 60 C CH3 C H C H2CH2 CH3 9H3 CH3 CH CI3H CH3 58 C CH3 9H3 CH3C CH2 CH3 50 C CH3 QHEMISTR Y L02 1 2 3 4 2 3 4 ALKENE NOMENCLATURE WORKSHEET fit sz C CH CH CH CH Cl 13 2 2 2 3 H3CcH CH2 H3C H3C CCH3 CH3 IUPAC NAMES FOR ALKENES ane replaced by ene ethane propene 2methylpropene Number carbons in longest chain containing both ends of the double bond Number from end with double bond having the lowest number For the double bond use the lowest of the two numbers CAHNINGQLDPRELOG PRIORITY RULES Partial lf atoms attached to a double bond end are different the atom with the higher atomic number has priority I Br Cl 8 F O N C D H lf atoms are the same the one substituted with atoms of higher atomic number comes first If equivalent in rule 2 the one with more substituents of the high atomic number comes first If second atoms out permit no choice third atoms out are examined etc E1 2 4 CahnlngoldPrelog Priority Rules If atoms attached to a double bond end are different the atom with the highest atomic number has priority gtBrgtCgtSgtFgtOgtNgtCgtDgtH If atoms are the same the one substituted with atoms of higher atomic number gets priority H lower OH O3H higher priority 39139 priority CH3 H lower 3NH 3CI higher priority 2 39139 priority If equivalent in rule 2 the one with more substituents of the high atomic number gets priority H H 9H3 3 H 3 CH3 3 CH3 H H H increasing priority gt If second atoms permit no choice third atoms out are then examined etc until a priority can be set 39 r r ltHs H 3 3 3 CH3 l3 C H2 C 3H H H H CH3 increasing priority gt Note Because rule 3 precedes rule 4 the priorities below are as pictured I 9H3 9H3 Emil ltelteCH3 lteCH3 Lil y H CH3 H p y E2
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