Survey of Organic Chemistry
Survey of Organic Chemistry CEM 143
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Date Created: 09/19/15
CEM 143 Summer 2009 Chapter 9 Study Guide Aldehydes amp Ketones Generic Structure 0 O RAH RJLR aldehyde ketone Nomenclature Aldehydes For acyclic molecules 1 Define the longest alkane chain that contains the CO 2 Remove e ending of the alkane eg methane becomes methan 3 Add al ending For example 0 i 2 carbons so ethane gt ethan gt ethanal H30 H ethanal Common name acetaldehyde 0 JL 1 carbon so methane gt methan gt methanal H H Common name formaldehyde For cyclic molecules 1 Use name of ring 2 Add carbaldehyde to end For example H Ring 2 cyclohexane so full name is cyclohexane carbaldehyde Ring 2 benzene so full name is H benzene carbaldehyde Common name benzaldehyde Ketones For acyclic molecules 1 Define the longest change that contains CO 2 Remove e ending eg methane becomes methan 3 Add numerical position of CO which gets priority in number over everything else we ve learned so far 4 Add one ending For example Longest chain 5 carbons to pentane gt pentan Position of CO is 2 so pentan2 CH3 Ketone so add one ending gt pentan2one Longest chain 4 with double bond so butene gt buten Position of CO is 2 so buten2 CH3 Ketone so add one ending gt buten2 one Add position of double bond which is 3 so 3penten2 one gg L Common Names for Ketones Naming is similar to ethers Name each side of the CO and add ketone at the end For example 0 CH3 ethylmethyl ketone ethyl methyl group group O methylvinyl ketone Vinyl methyl group group Some names you should know O O 0 CH3 0 0 methylphenyl ketone diphenyl ketone dimethyl ketone or or or acetophenone benzophenone 2propan0ne or acetone Synthesis of Aldehydes amp Ketones This is all review from Chapter 3 Chapter 4 amp Chapter 7 Aldehydes via Oxidation 0 P00 RAOH RJLH 1 acoho Ozonolysis H H 03 H H gt gt lt 2ZnCH3000H gt0 0 lt Ketones via Oxidation R39 0 P00 gt 39 R OH or CrOa HCI R R 20 alcohol Ozonolysis 1 Os 2 Zn CHacOOH O O Freidel Crafts Acylation of Benzene 0 Reactions of Aldehyes and Ketones This reaction is also review 0 COHC O L r3 A RH ROH Addition to 00 Common Nucleophiles sources that add to carbonyls REAGENT ADDS o 6 6 6 A HOH OH 6quot HOR OR The CO bond is polarized so H39CN ON the carbon with the 6 acts as M 0 0 R 00 R an electrophile Bng R R sink H3AlH H HZNR NR HNR2 NR2 General Addition Reaction Nuc39 Nucleophile source 0 6 O39 OH k 5 Nuc Nuc K Nuc Tetrahedral intermediate carbonyl carbon went from sp2 hybridized to sp3 so the shape went from trigonal planar to tetrahedral This is the general way most addition reactions happen For example 0 6 HCN OH 0 H A gt gt 7 K quotcyanohydrinquot C O 5 HOH l39 OH J gt 6 H O HO k H quothydrate or HOH geminal diolquot 1 CHsMgBr 039 2 H30 OH Jx 4 9 6 C 3 H30 OH 6 o O 1 LIAH4 2 H30 293 H gt H quotH This is a reduction reaction it reduces the number of C0 bonds LiAIH4 only works with polar bonds like COit does not work on nonpolar bonds such as CC Another reagent that does the same reaction is NaBH4 Nitrogen Compounds Addition followed by Elimination Nitrogen compounds behave a little differently than the reagents mentioned above The same core steps are involved however there are some differences For example H o 6 H 0 0 6 MOW HNCH3 Addition Now the 1 of a nitrogen The first step UC39eOPh39Ie Now we compound is protonation aHaCkS switch usually Includes of the carbonyl around an acid catalyst oxygen which the 39H39 to Also all the reaction makes the make a steps are in equilibrium carbonyl carbon new meaning that the more electrophilic leaving reaction can go back or a better sink group and forth this is called a quotproton transferquot HCO H Y Y 3 NCH H NJr CH Now the lone N 8 O O 3 pair of electrons H CH3 quotNEquot on nitrogen move H2O to form a pi bond Since this double bond reaction is and kick off the acid catalyzed we must end up with an acid in the end so the water grabs the extra H and forms hydronium water leaving group This reaction works for primary amines onlysecondary amines react essentially the same but have one more step which we will not wor about Tertiary amines typically do not act as nucleophiles but rather act as bases How do we tell the difference between primary secondary and tertiary amlnes H NH2 N N I primary secondary tertiary amine amine amine We figure out primary secondary and teritary amines differently than we do alcohols and alkyl halides Primary amines have 1 nonhydrogen group attached to them secondary amines have 2 nonhydrogen groups attached to them and tertiary amines have 3 nonhydrogen groups attached to them Types of nitrogen compounds that work like the above reaction r N R RNH2 gt primary A amine OH H2NOH N gt A hydroxyl amine A NH2NH2 N k hydrazine NHNH2 N gt phenyL hydrazine K Acetal formation General structure of an acetal RO OR Acetals are ways to protect carbonyls from reacting when you don t want them to How do we make acetals We add some alcohol with an acid catalylst O ROH H RO OR A This reaction proceeds just like imine fomation but with an extra few steps at the end A H H O ROH39 H O O Hemi U k acetal o not stable ROH H R Proton Transfer ROH FL H H H O 10 oR R 6quot O R H Notice that all these steps are in equilibrium so they are reversible o By adding H20 and H to the acetal R H20 we can go back to the ketone acetal Cyclic Acetals These work the exact same way except the aldehydeketone and the alcohol are contained within the same molecule For example A O H 1 OH 0H 3 WM V 3 1 2 H OH Cyclic hemiacetal These are stable Aldol Condensation This reaction is between two of the same aldehyde or ketone Before we can understand this reaction there are a few key concepts we need to learn If we are using two aldehydes like this 1 AOL we cannot react them because they are both considered electrophilic or sinks What we need to do is make one of them a nuoleophile or source The way we do this goes back to a key concept we learned in Chapter 3 This concept is called ketoenol tautomerization Remember anytime we added H and OH across atriple bond we ended up with a double that had an OH su bstituent We learned that anytime this happens the bonds always rearrange to form the CO as seen here O OH L H enol keto form form Also remember that CC are a source of electron density and are nuoleophilic So in order to do the reaction we want we need to force one of the aldehydes above into it s enol form We do this by using a strong base The base that we will use is called LDA lithium diisopropylamide shown below TNT The second concept that s important is that of the alpha proton and it s pKa When we talk about alpha protons we are talking about the hydrogen attached to the carbon NEXT to the CO as seen here pKa20 O pKa25 o Hv H CH H C T T H2 H2 T alpha proton alpha protons A base like LDA can pluck off one of these protons and force the molecule into it s enolate form like this 0 o C H TT lH H N charge instead of being L39 an OH like in the enol form Now we have a nucleophilic enolate and an electrophilic aldehyde and the reaction can proceed as below This is called the enolate form because the oxygen has a negative CEM 143 Summer 2009 CH 10 Study Guide Carboxcylic Acids and Their Derivatives Overview Chemistry of acids parallels that of aldehydes and ketones but with an added step Aldehyde JOL o H gt HO H R H R RJlt OCH L HI 3 o CH3 H O CH3 THE NET REACTION ABOVE IS AN ADDITION REACTION Acids amp Derivatives o O x Htof o RJLX RgtltOICHS gt R ltX R OCH3 k HI o CH3 H O CH3 X acts as a leaving group THE NET REACTION ABOVE IS A SUBSTITUTION REACTION What can X be 0 L Cl OH NHR OR O R Naming Acids Many carboxylic acids have common names butyric acetic valeric etc based on their source I will only expect you to know how to name generic carboxcylic acids and the special ones that show up on this sheet When naming a carboxcylic acid we name them using the same rules as aldeydes except we use a different ending The ending we use is oic acid For example 2 carbons ethane e ethan proper ending i ethanoic acid H3O OH Common name acetic acid vinegar 0 In an aldehyde with cyclic systems we named the ring in this case benzene and added carbaldehyde at the end OH For carboxycylic acids we add quotcarboxcyclic acidquot at then end to give Benzene carboxcylic acid Common name Benzoic acid Other carboxcylic acids you should know 0 o OH OH O OH OH O terephthalic acid phthalic acid Used to make PETE plastics Used as a plasticizer in PVC plastics Ph sical Pro erties of Carboxc lic Acids Carboxcylic acids do acidbase chemistry O O H2O H O LOH A0 3 T pKa 17 pKa 48 Stronger acid than an alcohol but not strong enough to be considered one of the 7 strong acids so it doesn39t dissocaite 100 in water But if we use a strong base 0 O NaOH gt H2O A OH LO39 Na acetic acid sodium acetate 0 O NaOH H20 OH O39 Na benzoic acid sodium benzoate Just like with phenols when we add electron withdrawing groups such as halides the acidity increases 0 o o o LOH CIQLOH C39 ILOH glykon CI CI pKa 48 28 13 07 quot quot 39 of Ca Acids Oxidation of 1 alcohols with CrO3 amp acid 0 Cr03 gt OH LOH Via Grignard Reagent 1 002 O MgBr gt 2 H30 JkOH How does it work 0 H30 O gt gt 0 C8 JkCJ MgBr JLOH MgBr This is very useful on aromatic rings as well Br Mgo MgBr 1 CO2 OH gt ether 2 H30 Via KMnO4 amp heat Remember that KMnO4 cool dilute oxidized CC KMnO4 HO OH cool dilute j I For aromatic rings with alkyl groups on them the alkyl group gets fully oxidized CH3 KMnO4 O OH heat A And it doesn39t matter how long the alkyl chain is KMnO4 O OH heat A Or how many alkyl groups are on the ring KMno4 gt heat A HO 0 OH
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