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Review Sheet for CHEM 3331 with Professor Thummel at UH


Review Sheet for CHEM 3331 with Professor Thummel at UH

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Date Created: 02/06/15
Review ofOrgam39c I Chem 3331 l CHEMISTRY 3332 ORGANIC II Review Wade Chapters 113 See wwwchemuheducoursesthummelChem333 lWade REVIEW Chapter 1 Intro amp Review Consider a simple picture of an ATOM Nucleus consists of Mass Charge Protons 1 1 N Neutrons 1 0 V Electron ca 0 l Isotopes of an element have different numbers of neutrons in their nucleus For example 12C has 6 protons 6 neutrons 13C has 6 protons 7 neutrons 14C has 6 protons 8 neutrons t12 5730 years tell ages up to 50K yrs This picture for the nucleus is OK but not so good for the electrons They cannot be represented as point charges This problem was solved by the birth of quantum mechanics Shapes 0fAt0mic Orbitals 3 types s p d ls orbital is lowest in energy and closest to the nucleus Y Z S orbital spherically symmetrical p orbitals have a node at the nucleus and two lobes which extend on either side Review ofOrgam39c I Chem 3331 2 Porbital has a node at the nucleus Y Z Y Z Y Z 2px 2py 2pz Rules for Filling Atomic Orbitals 1 Aufbau Principle orbitals of the lowest energy are filled first 2 Pauli Exclusion Principle only two electrons can occupy the same orbital and they must have the opposite spins 3 Hund s Rule if two or more empty orbitals of equal energy are available one electron is placed in each until all are half full Energy Levels of Atomic Orbitals Energy Levels of Atomic Orbitals High 4d 55 T 4p 3d E 48 These 24 orbltals can nergy account for the first 3P 48 elements 35 2P 25 Low 15 Chemical Bonds are the forces that hold atoms together in a molecule N ote energy is always released when a bond is formed ie a more stable lower energy situation results 1915 G N Lewis proposed the quotoctet rulequot Atoms will tend to transfer or share electrons to acquire a stable complete outer shell configuration similar to He Ne and Ar This leads us to the two types of chemical bonds Review ofOrgam39c I Chem 3331 3 l Ionic Bonds result from the transfer of electrons creating oppositely charged species which then attract one another Ionization Energy tendency of an atom to loose an electron quotElectropositivequot elements ie Na sodium have low IE and hence can easily loose an electron to become positively charged Electron Affini tendency of atom to gain an electron quotElectronegativequot elements lie F uorine have low large negative EA and hence can easily add an electron to become negatively charged Sodium Fluoride N aF How about carbon 2 Covalent Bonds result from the sharing of electrons to give a complete outer shell configuration Designate this process using Lewis Dot Structures H methanol HCOH These are called I Kekule structures H Formal charges when an atom looses an electron in forming a covalent bond it acquires a when an atom gains an electron it acquires a a consider the protonation of water A H 0 now has only 5 electrons H6H H gt H o H Haslost1e39 O has 6 electrons Notice how we use curved arrows to designate the movement of 2 electrons These arrows do not show the movement of atoms VERY IMPORTANT Polarization symmetric polar ionic c o v a e n t b o n d c W a e n t b o n d b o nd gt 22 NH nnnnnnn ce n39d Review ofOrgam39c I Chem 3331 5 5 The more resonance forms the better AcidBase Theory 1 Bronsted LOW139y Definition Acid proton donor Base proton acceptor K HA H20 2 H3o A39 Conjugate base ofHAj Acid Base HO A39 t HA H20 f HA Large constant Acidity Constant pKa log Ka The stronger the acid the lower the value of pKa Explain Lewis De nition Acid Electron pair acceptor This is more general and covers the Base Electron pair donor Bronsted def but also includes others H4 u H or HOH H O H Acid Base quot Eraw Fxg W3 r 9 of la 39 IMO F Cl F F l 9 CH3 F CH3 Acid Base In general Compounds with N O are good Lewis bases because they have lone pair electrons which they can donate Note Another name for Lewis acid is electrophile electronloving Chapter 2 Structure and Properties of Organi cccccccc es molecular 0rbi ttttt O Review ofOrgam39c I Chem 3331 7 2p l 6 25 C How can carbon form 4 bonds 15 if it has only 2 unpaired electrons to share 2 1 promote 25 gt2p 25 1sH l hybridize mix Spa 44 mix together 3 2p and 1 25 orbital to get 4 new orbitals we call spa 2pl 1s Shape of new sp3 hybrid Mil ill l W Dentin meugigiiiiil Arrange four of these so that they all originate from a common point and are oriented as far apart as possible They point to the comers of a regular tetrahedron Ethylene sp2 Hybridization The carbons in ethylene C2H4 are each connected to 3 other atoms The fourth valence of the ethylene involves a CC double bond H C C H H How do we explain this structure in terms of orbitals w ofOr Chem 3331 6c 2p L l 2p is ooooooo 2s J 4 s gt 4 Hybridize h 0 3444 4 h HCECH How do we explain this structure with orbitals Acetylene sp Hybr The carbons in acetyl lllllllllllllllllllllllllllllllllllllllll lllllllllllllllllllllllllllll as possible Review ofOrgam39c I Chem 3331 9 Rotation about Bonds Isomers There is free rotation about the central CC bond of ethane the CH bonds on one carbon may be eclipsed or staggered with respect to one another H H H H H H H H H CONFORMERS OF H H SAME MOLECULE Staggered Eclipsed Structures which differ only by rotations about single bonds are called conformations Dipole moments and the forces that attract molecules We have learned about the planarity of bonds and how to compute the dipole moments of molecules How can intermolecular forces attractions or repulsions help us to understand the 3 states of matter gas liquid solid Dipoledipole interactions cause attractions between polar molecules These forces must be overcome in melting or boiling What about nonpolar molecules Why do larger molecules have higher BP and NIP This is due to van der Waals forces These result from temporary dipole moments due to the uneven distribution of electrons Hydrogen Bonding A hydrogen atom can participate in Hbonding if it is bonded to O N F Since no molecules contain HF we consider only 0H and N H OHOC worth about 5 kcalmole CONSIDER HSC CHzOH H3C O CH3 ethancll dimethyl ether bp 78 C bp25 C These functional groups can be grouped into three general categories 1 Groups with CC multiple bonds clt czo Alkenes Alkynes Arenes Review ofOrgam39c I Chem 3331 10 2 Groups with carbon singly bonded to an electronegative atom I I I I X OH C O C f 00 f 00 I 00 I Alkyl halide Alcohol Ether i iSH W Amine Thiol Sulfide 3 Groups with a CO carbonyl group I i I 9 I I 9 C CH C C C c C OH AldEhYde KGtone Carboxylic Acid I II I I 9 c c o c C C N 00C I Ester Amide Acid chloride Chapter 3 The Structure and Stereochemistry of Alkanes T T T T H IZ ll IZ IZ H Same as IZHZ CH3 I3H3 H H H H CHs C H3C CH2 C H2 H2 Butane Table 31 nAlkanes LEARN NANIES OF FIRST 10 Think about next 10 CH4 methane CH3CH3 ethane CH3CH2CH3 propane Review ofOrgam39c I Chem 3331 ll CH3CH22CH3 butane pentane General formula CnH2n2 hexane heptane Homologs differ only by number octane of CH2 groups nonane CH3CH28CH3 decane Isomers are compounds with the same molecular formula but different chemical structures Butane 2 isomers Heptane 9 draw them Decane 75 C 1 5H32 4347 C40H82 6249117880583l isomers IUPAC Nomenclature Rules for Alkanes 1 Find the longest contiuous carbon chain and use this name as the base a If two chains of equal length are present choose the one with the more branch points as the parent 2 Number the longest chain beginning with the end nearest a substituent number structure above 3 Name each substituent group and assign it a number a If there are 2 substs on the same carbon they both get the same number 4 Write out the name substituents come in alphabetical order use di tri tetra for multiples of the same subst 5 Name any compleX substituent For example H3 H3 CH3CH20HZCH2CIII CHCH3 H2 H3 CHz CH3 2Methyl5l2dimethylpropylnonane Review ofOrgam39c I Chem 3331 12 Alkyl Groups alkanes in which a hydrogen has been replaced by another group CH3Cl methyl chloride change quot anequot to quot ylquot CH3 methyl CH2CH3 ethyl CH2CH2CH3 npropyl H3 HgC CH Isopropyl CHgCHZCHzCHZ nbutyl ch CH CHzCHg secbutyl CH3 HSCCHCH2 isobutyl i H30 CH3 tert butyl or t butyl HSC CHZ neopentyl CH3 H H R C H primary carbon 1 R C H secondary 2 I one substituent H R R R RCH tertiary 3 R C R quarternary 4 R R T so if We talk about a tertiary alcohol We mean R T OH R Reactions of Alkanes gtCHC H3 H3 CH CH CH3 H H H 3 H H3 3 H CH3 3 H H H H H H H CH3 H30 H H H H H H H Anti Eclipsed Gauche Eclipsed Gauche 1 mirror image Review ofOrgam39c I Chem 3331 14 When 2 different alkyl groups are present number alphabetically Halogen substituents are treated like alkyls CH3 lbromo2methylcyclobutane Br When the acyclic portion of the molecule contains more carbons than the cyclic part or when it contains an important functional group the cyclic part is named as a cycloalkyl substituent give example Br Br Br H H H cis12dibromocyclopropane trans12 Stereoisomers j Nature of Ring Strain 1 Angle strain due to eXpansion or compression of bond angles 2 Torsional strain due to eclipsing of neighboring bonds 3 Steric strain due to repulsive interaction of atoms approaching too closely 1 Cyclopropane H six pairs of eclipsing interactions Jr A H X I 115 4 increased over 1095quot H more pcharaoter weaker bond a 5 iii ttttttttttttttttttttt es t r a n s c Is Review ofOrgam39c I Chem 3331 16 In fact the two conformers are nonsuperimposable mirror images of one another hence we have conformational enantiomerism later a La Methylcyclohexane Gauche interaction Ha H3 CH H CH H N H H ltH2 CH3 HE C 2 H H no gauche interaction Note one axia HHa at 25 C 95 18 kcalmole interaction 09 kcalmole f f m re Stable What is he relationship D0 same analysis for 13 and l4dimethylcyclohexane Chapt 4 The Study of Chemical Reactions Mechanism is a complete stepbystep description of the bond making and bond breaking steps in a reaction depends to a large extent on Thermodynamics study of the energy changes that accompany a chemical reaction Relates to product amp reactant stabilities and equilibrium Kinetics study of reaction rates how fast reactions occur Reactions can be organized in 2 ways Review ofOrganic I Chem 3331 17 1 What kinds of reactions occur 2 How reactions occur Consider 1 first kinds of reactions 1 Addition reaction A B gt C H r H HBr licltf gt H e i H H H M Bromoethane 2 Elimination reaction A gt B C reverse of addition H Br H E YS H gtNaoH HtccH HBr H H H H 3 Substitution reaction A B gt C D H H H H CICI gt H CI HC H H Chloromethane 4 Rearrangement reaction A gt B H catalyst CH30H20HCH2 gt CH3CHCHCH3 Consider how reactions occur MECHANISM detailed stepbystep description of a reaction describes all bondbreaking and bond making processes Bond breaking and making can occur in two ways 1 Homolytic bond cleavage radical one electron to each fragment AB A B 18 Review ofOrgam39c I Chem 3331 2 Heterolytic bond cleavage polar two electrons to one fragment A B gt A B 39 Chlorination of methane is a good example what is the mechanism H I H C H CICI gt HCCI HCI I H H l Initiation 1 xxx 39 ht quot XX 3gtlt39Cgtlt lg gt Cl39 XCI 2 chlorine radicals XX or heat quot XX 2 Propagation 0mm 043 Hj CI CH3 Clo l H39 1 CH3 CIICI CICH3 Cl Lu repeat over and over overall process is a chain reaction 3 Termination A CI 0 CI2 cro quot CH3 CI CH3 3ICH CH3CH3 lt not productive Polar Reactions In polar reaction the electrons move in pairs Why We have said that certain bonds can be polar Review ofOrgam39c I Chem 3331 19 liq e if we break this bond HEC39C39 e39 tend to go with Cl H 4 CH 3Br Mg H CMgBr Ifwe break thls bond H 539 5quot e39 tend to go with C H Hbm Hg6rH e39 tend to go with oxygen to give H H39 H neutral H20 Equilibria amp Rates or Thermodynamics amp Kinetics aAbB CCdD CHDId kf q AFN3b kr K large gt lies to the right This is a thermodynamic K small gt lies to the left property it tells nothing about how fast equil is established only the final mixture It may be expressed as AG RT aneq R gas const 1987 cal degkelvin mole T absol tempdeg kelvin e 2718 Discuss signs K 1 AG 0 K gtl AG negative exothermic Kltl AG positive endothermic AH AH bonds broken AH bonds formed negative exothermic positive endothermic Review ofOrgam39c I Chem 3331 20 Thermodynamic info tells us nothing about the w of reax Energy CH4 c1 25 kcal mole l CH3C1 HCl Progress of Rx Rate P Z eEact RT 2 P ZeEactRT Look at Reaction Coordinates Potential Energy Diagram Potential Energy Em 2 H positive Progress of Rx gt Notice that there is an energy barrier Activation Energy even for exothermic processes Some reactions have more than one step between each step an intermediate is involved represented by a minimum on the rxn cordinate stability of an intermediate is a function of the depth of this well k1 CI202 CH4 c1 lt gt Hc1 CH3 gt CH3Cl c1 1 reactant intermed K2 prod uct Review ofOrgam39c I Chem 3331 21 CH3C1 Product Reaction Progress gt The lower the energy barrier E act the larger the rate constant k Thus for the above k2gt k1gt k1gt k2 Isotope Effects Deuterium is the isotope of H with mass 2 The CD bond is slightly stronger than the C H bond and hence harder to break Reactions which involve CD cleavage go slower than CH CH4 C1 gt CH3C1 HC1 rel rate12 CD 4 Cl y CD3C1 DCl rel rate 1 Halogenation of Higher Alkanes Most alkanes give mixture of products book give propane amp gets slightly differant selectivities 30 70 v CHsCHzCHZCHs C2 gt CHsCHzCHZCHZCI CH3CH2CHCH3 1chlorobutane 2chlorobutane 943 hv 943 943 CH 3 c H 0392 gt CH 3 c C CICH 2 Cl3H CH3 CH3 CH3 35 65 Review ofOrgam39c I Chem 3331 22 By taking into account actual product ratios and number of each type of H we can calculate relative reactivities of the 3 types 1 2 3 of hydrogens towards chlorination Relative reactivity toward chlorination R3CH gt R2CH2 gt RCH3 50 35 10 Look at PE diagrams for these two processes close in structure dose in structure angy and energy products reactants products reactants Hammond Postulate Related species that are similar in energy are also similar in structure The structure of a transition state resembles the structure of the closest stable species Reactive Intermediates short lived species that are never present in high conc because they react as quickly as they are formed T T T H c H C H CI H c3939 H H H r Carbocation Radical Carbanion Carbene Carbenes T13 A Ti Br f H oH p H2O Br fr gt gr f Br Br Br Br Tribromomethane Camanion Dibromocarbene Review ofOrgam39c I Chem 3331 23 Empty porbital Nucleophilic amp Electrophilic Nonbonding electrons Chapter 5 Stereochemistry Refers to structures in three dimensions Polarimeter monochromatic light Na D line 5893 A fpolarizing filter quotAnalyzer A eye hence CL 0c gt observed measured rotation 1X c As predicted miror images nonsuperimposable of organic compounds do exist COOH COOH CH3CH CHZCHs HKD39OH GHQ H3 CI CI QH CH3 CH3 CH3 CH3 Lactic Acid sec butyl chloride Enantiomers Optical activity Chirality Chiral center Stick figure representation of a chiral molecule Fisher projections later Review ofOrgam39c I Chem 3331 24 CHSCH CH3C 2 HZCH3 H CI H CI CI H CH3 CH3 CH3 R amp S convention I For a chiral carbon use the CahnIngoldPrelog sequence Rules to assign priorities to the 4 groups a Rank atoms in order of decreasing atomic number b If 2 atoms are the same work outward to the first point of difference c Muliply bonded atoms are considered as if they were an equivalent number of singly bonded atoms 2 Orient the molecule so the lowest priority subst 4 is pointing away from you Look at the three remaining groups lgt2gt3 clockwise R 1gt2gt3 counterclockwise S For example 1 4 QHCH 2 1 t1 3 4 H39Q 3 HOYCH 3 8 configuration CgoH COOH 2 Lactic Acid Diastereomers Look at a molecule that has 2 adjacent chiral centers 23dichloropentane CI CI i i CH3CHCHCH2CH2 23 dichloropentane Book uses 2bromo3 chlorobutane Draw con gurations Review ofOrgam39c I Chem 3331 25 3 CH3 1 CH3 5 H c CI H R 1 3 CI H H CI R CH 30H 2 CH 2CH 3 3 Enantiomers Now let s change configuration of only one carbon CH3 CH3 S R H CI cl H R CI H CI 5 CH 30H 2 CH 2CH 3 Enantiomers Each member of this pair is a diastereomer of each member of the first pair Meso structures Now let s look at 23dichlorobutane CH30IlI clH CH3 CI CI 2 adjacent chiral centers let s draw configs again CH 3 CH3 3 H CI CI H S Cl H H CI CH3 CH3 Enantiomers Review ofOrgam39c I Chem 3331 26 Change configuration of one carbon CH3 CH3 8 H CI Cl H Book does this for cis 12 dichlorocyclopentane R H lm CI H Q CH3 CH3 H H Superimposable gt a meso compound Meso Compound one whose molecules are superimposable on their mirror images even though they contain chiral centers Racemic Mixture a mixture of equal parts of enantiomers5050 Optically inactive for every molecule giving a rotation there is another which gives net sum 0 Use prefix i H3 H 3 CH H H CH3 very fast at room temp 392 hence no optical activity H H HHH Gauche n Butane Fisher Projections l A Fisher projection can be rotated by 180 but not by 90 or 270 OOH 180 CH3 90 H H OH HOH I Hsc i COOH CH3 COOH OH 2 Hold one group steady and rotate the other three clockwise or counterclockwise Hold steady OOH COOH Z HO i CH H OH H 3 CH3 Rotate these 3 Stereochemistry of Chemical Reactions Review ofOrgam39c I Chem 3331 27 1 Reactions at a chiral carbon 2 Reactions that do not involve the chiral carbon 3 Reactions that generate a new chiral carbon 50S p f BrBr CH3CH2 CH3 tltp Br CH CH CH CH gtCH CH 3 2 2 3 3 2 39CH3 0 2 Bromobutane planar radical achiral Br V 50 R r CH3 Stereochemistry in cyclohexanes cis CH Wm chmCHg Meso H H H H trans H CH 3 CH3 H Enantiomers CH3 H H CH3 Chapter 6 Alkyl Halides Nucleophilic Substitution and Elimination Nomenclature 1 Name as halo alkanes 2 Name as Alkyl halides 3 Common names CI quotquotCI 11dibromoeyelohexane trans12 diehloroeyelohexane A geminal dihalide A Vicinal dihalide Review ofOrgam39c I Chem 3331 28 Polar bond 75 C has 5 hence good electrophile Preparation of Alkyl halides l Halogenation of alkanes 2 Allylic Halo genation Allylic pH H H Br hv B gt Q r2 CC4 Q HBr H H H H 3bromooyolohexene O 85 o N Br 639an 0 o Nbromosucoinimide NBS Allylic radical is stabilized by resonance H H quotH39 H H H H NBS Fer o CH3CH24CH20HCH2 WH3CH24 CH CHCH2 174 1 Octene 3bromo1ootene CH3CH24 CHCH CHzBr 83 1bromo2 ootene Reactions of Alkyl Halides Nucleophilic Substitution and Elimination Nucleophilic e quot Subst CH3Br 29H gt CH 39H Br 9 Nucleophile Review ofOrgam39c I Chem 3331 Elimination 29 H30 CH3 e2 H gt Hep 3042 H20 i rze CH3 Base CH3 SN2 Reaction SuBstitution nucleophilic 2nd order 4 v e 1 a r39 Nuzegt X gt NUIIIIIIICIIIIIIIX gt Nu C X16 Transition State 1 Stereochemistry 2 Kinetics Rate k39 OH CH3Br 3 Energy diagram one hump no intermediate Nucleophile Product H hydride Hsc Br gt CH4 0 e H3C a methanethiolate gt H3C S CH3 H S e hydrosul de gt SH CH3 thio39 e N C cyanlde gt NC CH3 nItrIIe e iodide gt I CH3 e HO hydroxide HO CH3 aICOhOI H3O u e methoxide gt HscOCH3 Ether NN il e azide Ns CHs CI 6 chloride gt Ci CHs O H33 C Oe acetate gt Hsc H O CHs ester 39NH ammonia gt 63 6 3 H3N CHsBr Let s examine the effect on the rate of SN2 reaX of l Nucleophile Nu Nucleophilicity roughly parallels basicity See table 63 p 246 2 Solvent Review ofOrgam39c I Chem 3331 30 3 Subtrate Alkyl group R Crowding raises energy ofTS 39 quot and slows dovm reax 4 Leaving Group X A leaving group is expelled with pair of electrons R 2 X ability to stabilize these electrons 2 better leaving group Note 8N2 only occurs at sp3 carbon not sp2 Nu ga f 390 x gtNR CI x gt NR x R R Nu The SNl Reaction substitution nucleophilic rst order R 1 1 H3 CH3 A I ch c Br i H30C Ere CH3 CH3 Carbocation intermediate 2 CH A 3 H l T seaCH3 H30C CHg ZDz H gt Hgo c ol CH3 CH3 H Final deprotonation Stereochem reaction occurs with almost complete racemization Review ofOrgam39c I Chem 3331 31 Cl 330 39Br Potentral B CH OH Energy 3 03 CH3 OCH3 Reax ProgreSH Carbocation Rearrangements When a more stable carbocation can be formed by the migration of a hydride H with 2e or CH3 this process will occur some of the time leading to rearranged products Br QCHZCHg OCHZCHg I CH CH OH I CHg CHCIH CHg gt CHs39CHCIH CHs CHg CHz Q CHg HBr CH3 2 CH3 CH3 Not rearranged Rearranged Eliminations There are 2 types of eliminations similar to substs El CH3 H3 CH3 39 111 step 2 CH3 3 CI slowgt CH3 Che fast C CH2 BH CH3 H20H CH3 Be carbocation intermed T31 T32 l E H Reac ion Coordinate gt Note No deuterium isotope effect would be observed because CH bond not being broken in slow ratedetn step OH CH IHCH3 gt A CH3CH3 Br 19 E2 eliminations are often stereospeci c mesa12dibromo12dipheny1ethane gives only Elbromo12dipheny1ethylene B39 H gt Br H HA 39 gt cc Br Br Cf 23 Br Br More apparent in cyclic systems Deuterium Isotope Effect more evidence for E2 C D bond is stronger than C H broken in RD step Review ofOrgam39c I Chem 3331 33 K H HC CHltH m H spZsp3 W 1501 A mm c m gt 1103 A C a 1112 A Degree of saturation How many rings and or C C are present i e C4H8 one degree of unsat c cc or B should be able to do by inspection C4H6 2 degrees Czczc C or ID Nomenclature of Alkenes 1 Pick the longest continuous carbon chain containing the double bond Name this as an alkane but change quot anequot to quot enequot 2 Indicate the postion of the double bond in the parent chain by by using the number of the first doublybonded carbon when numbering from the end nearest the double bond 3 Indicate by numbers the position of the alkyl groups attached to the parent chain Rules in book 943 H CH3 CH3 CHCH2 CH3 CH H CH3 EH 33dimethyI1butene CHs trans4 methyl2 pentene Cycloalkenes remember cis and trans E Z Nomenclature Review ofOrgam39c I Chem 3331 34 EH3 Pk HCH2 CHs CHCBr c H c H CH3 CH3 2 H E 3methyI13pentadiene E 1br0m02i89pr0pyl1r3 butadlene Bredt39s Rule A bridged bicyclic compound cannot have a double bondat a bridgehead position unless one of the rings contains at least 8 carbons Preparation 0f Alkenes elimination reactions 1 Prefer E2 because it avoids carbocation intermediates 2 Dehalogenation of Vicinal dibromides Not a very useful reaction since Vicdihalides often made from alkenes Nam r acetone 39839 NaBr I BA Zn gt ZnBr2 CH3000H Dehydration of alcohols El A OLOH H2304 CSHZ dad i r 3 R Possible rearrangement Review ofOrgam39c I Chem 3331 35 Reaction Mechanisms Try this one H2OH H2 H3 H2804 5 a g E 6 heat show every step show electron ow with arrows Chapter 8 Reactions of Alkenes Electrophillic addition Electron rich nbond reacting with electron poor species A strong electrophile has an affinity for the loosely held selectrons WNW m CI39 0 H HCI C3st CHKM H slow CHs carbocation fast Carbocatlon trivalent carbon only 6 electrons positive charge cl CHg lCCHg CH3 Markovnikov39s Rule In the addition of HX to an alkene the H always bonds to the carbon with more hyrogens and the X bonds to the carbon with more alkyl groups E CH3 CH3 Br H HBr H ether Stability order for carbocations 3 gt 2 gt 1 gt methyl Hyperconjugation R some overlap R iH some delocalization of charge H more such overlap possible for more CH subts adjacent to C rather than just H Review ofOrgam39c I Chem 3331 36 Addition Reactions of Alkenes 1 Addition of Hydrogen halides also free radical a ionic mech Mark s Rule b radical mech CHs39C39CH HBr 393H3 P CH 2 perOXIde CH3 CH CHZBr isobutyl bromide 2 Hydration direct acid cat addition of H20 is poor Oxymercuration Demercuration Markovnikov amp Anti addition Hydroboration oxidation AntiMarkovnikov amp Syn addition 3 Catalytic Hydrogenation 4 Cyclopropanaton carbene addition to alkenes Singlet and triplet carbenes CI C lt gt CI 0 singlet carbene triplet carbene eleCtronS Palred electrons unpaired Dichlorocarbene CHCl3 KOH Simmons Smith Reaction H O 0sz CHZ m i Bicyco410 heptane 59 5 Addition of halogen Stereochemistry bromonium ions 6 Halohydrin formation OH CHCH2 NBS IDH CHz Br H20 DMSO 7 Epoxidation Review ofOrgam39c I Chem 3331 37 Acid Catalyzed opening of epoxides Leads to anti 12g1ycols Wf sw C EIF IF H20 H20 H OH 8 Hydroxylation Leads to Syn 12glycols Use KMnO4 Potassium permanganate or OsO4 Osmium tetroxide Oxidative Cleavage of Diols O 001OSO4 HIog 2 O 2 NaHso3 9 Ozonolysis CH3 0 CH 44 Cgto CH3 2 Megs CH3 CH2 CH 1 O 3 O CH 2 Mezs 043 OCH2 Bipinene formaldehyde 10 Dimerization polymerization of Alkenes FH2SOA pHs P H3 CH3 H 3 H c H30 pH3 2 c CCH3H2CC H HsoiCHrq CH3 CH3 CH3 1 H H3 H H DIMER Hw T CHLC 3 mick cf CH3 CH3 CH3 CH3 30 20 Review ofOrganic I Chem 3331 38 Chapter 9 Alkynes Nomenclature 1 Common names derivatives of acetylene where hydrogens have been replaced by other groups 2 IUPAC names terminal alkyne ends in CH such as lbutyne above internal alkyne has 2 substs RCECR Acidity of Alkynes terminal alkynes R CECH are weakly acidic k R CC l H NHZIg gt R CC9Na HN39H2 Sodium acetylide Synthesis of Alkynes 1 Alkylation of Acetylide Anions SNZ 01 1 1 RX HCECzNa JCHZCHZCHZCH3 gt HCECCHZCHZCHZCHS l39 Na39 1iodobutane 1hexyne Works only for 1 Rx otherwise get elimination 2 Addition of Acetylide Ions to CO Group 0 OH Na 39CCH 6 H30 CH 3 Dehydrohalogenation Review ofOrgam39c I Chem 3331 39 Br r IBr O CH H CCI4 39 O CH CH Q 12 Diphenylethylene 12 dibromo 12 diphenylethane stilbene a vicinal dihalide 2KOH 2HBr EtOH E 2HBr u GHQ Br 11dibromo12 diphenylethane diphenylacetylene a geminal dihalide Reactions of Alkynes reaX Of the CiC bond 1 Addition of Hydrogen reduction to alkanes a Catalytic hydrogenation gives alkane or cisalkene 2H2 RCHZCHZR PdC R CC R E cis Lindlar catalyst C G R R Pd Barium sulfate Quinoline poisoned catalyst b Metalammonia redyction gives transalkene ULiNH3 R trans gt R C C R 2H20 R ED 2 Addition of X2 I39 I39 H3 Br T T Br H3CCCH rcvl4gt gt lt 7 gtcc14 ch IZ TH Br H Br Br E12dibr0m0pr0Pe e 1 12 2Tetmbromopropane major Can be stopped at this stage dflOHD TVNOILON d AleLNEICH SCIHVAAHOVEI IHOAA DDDDDDDDDEDDDDDD euequAwegsgp H8 Haza H a HQZH09ZHQ9HH HO H o ewnpuooese HQZH ppe JOUUEO OZH 2 Ho N H 9ZHO HO IHJ 9z 9 H H958 HOO HO HO Zaaj H DDDDDDDJODDDDDDDDDQDDDDDDDDDDDDID DEED DDSUBBEDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDD DDSUBBEDDDDDDDDDDDDDDDDDDDDDDDDDDQDDDDDDDD 1syx91ou seop 91q21sun 39IONEI ep qepmeoa 101102 Kmx 39deld emsnpug mellodul V 3 9 v Ho QH OS H H O O H vo z z S H lt0 H H3 3H LI HlH ammmmmmmmmmmmmmgmmmmmmmmi emexeqoulmquz z Ja gHo ol 9OZH09H T 18 SHSXSII OLIIOIqZ HZOOEHO ZHJ OszgH 18H H 09ZHo 09H 1i XHJOUOHWPV 017 1555 1442110 azuv xofo Mama Review ofOrgam39c I Chem 3331 41 Chapter 10 Structure and Synthesis ofAlcohols Nomenclature 1 Name the longest continuous carbon chain containing the OH Drop The quotequot and add quot01quot 2 Number the longest carbon chain starting at the end nearest the OH and use the appropriate number to indicate the position of the OH 3 Name all substituents and give their numbers 1chloro33dimethyl2 butanol Cyclic alcohols are named using the prefix cyclo the hydroxy group is on C1 39539 OH H o transZchIorocyclohexanol The OH group maybe named As a hydroxy substituent Boiling Points of Alcohols H H w y C H CHch3 H3 CH3 Hsc CHs Ethano39 Dimethylether Propane MW46 MW45 MW44 bp 78 C bp 25 c bp 42 C hydrophilic meaning quotwater lovingquot hydrophobic quotwaterhatingquot Acidity of Alcohols and Phenols A strong base can remove the hydroxyl proton to give an alkoxide ion Review ofOrgam39c I Chem 3331 42 H Ka 103913 H20 z H30 Cyclohexanol H Ka103910 39 H o z H30 2 Ph and Ph enoxide Synthesis of Alcohols l Nucleophilic substitution on an alkyl halide or tosylate Chapt 6 2 Oxymercurationdemercuration 3 Hydroboration oxidation 4 Hydroxylation 5 Organometallic Reagents for Alcohol Synthesis lt C M 539 5 RX Mg CchHzOCHZCHg RMgx X Cl Br or I organomagnesiom halide Grignard Reagent RX 2Li CHscHZ39O39CHchs RLi LiX X Cl Br OF I or hexane organolithium reagent Addition of Organometallic Reagents to Carbonyl Compounds 55 m Rm R O RMZ O gt 39R O MgX L 39R ID OH XMgOH R 5 5 R I R 1 Reaction with Formaldehyde gt 10 ROH Reaction with Aldehydes gt 20 ROH Reaction with Ketones gt 30 ROH Addition of Grignard Reagents to Acid Chlorides and Esters Addition of Grignard Reagents to Ethylene Oxide Corey House reaction uses an organocopper reagent a lithium dialkylcuprate to couple with an alkyl halide Review ofOrgam39c I Chem 3331 43 Li H H HgoCHzf Cl H30 0H2f CuLI E W CH3 2 DUI 2 CH3 3 th lh t 2chlorobutane lithium dialkylcuprate m Y 6P ans OgtltBr CHmCuLi OgtltEH3 H Br EtOEt 3 65 Side Reactions of Organometallic Reagents 1 Reactions with Acidic Compounds 2 Reactions with Electrophilic Multiple Bonds We must be sure that there is only one reactive group in the molecule Avoid quotwishfulquot organic synthesis Reduction of the Carbonyl Group Synthesis of Primary and Secondary Alcohols l A R o H30 f H C 039 H C OH R39 I R Alcohol 39i 39i Na H 39 H Li H fth H H 30mm b r hyd de Lithium Aluminum Hydride NaBH4 is more selective than LAH 7 reduces ketones in the presence of esters Thiols are sulfur analogues of alcohols with an SH group in place of the alcohol OH group CH3 SH CHaoH20quotl2CH239mSH HSCHZCH2OH methanethiol 1butanethiol 2mercaptoethanol methyl mercaptan nbutyl mercaptan A A Na HS RX gt RSH NaX Sodium hydrosulfide Thiol RSH HSR RSSR 2HBr Zn HCI Review ofOrgam39c I Chem 3331 44 Chapter 11 Reactions of Alcohols Oxidation of alcohols leads to ketones aldehydes carboxylic acids OXIDATION loss of H2 or the addition of O or 02 REDUCTION addition of H2 or H or the loss of O or 02 OXIDATION H OH I O I O E 0 H RIH R3H R39C39H RcOH H H No bonds to o 1 bond to o 2 bond to 0 3 bond to o Alkane 1 alcohol aldehyde carboxylic acid REDUCTION 1 Oxidation of Alcohols l Oxidation of Secondary Alcohols to ketones H O N820r207 gt H2804 2 Oxidation of Primary Alcohols Chromic acid strong conditions oxidizes all the way to carboxylic acid CHZOH COOH Na20r207 H2804 Partial oxidation with PCC forms an aldehyde 0 PCC AjOH gt H 3 Tertiary alcohols do not undergo oxidation normally Review ofOrgam39c I Chem 3331 45 Alcohols typically react by breaking either the 0H or the C0 bond Break this bond and the reak this bond and the Clcohol reacts as a nucleophile alcohol reacts as a electrophile l 3 O H 3 O H Since OH is a poor leaVing group we can convert it into a better one by preparing the tosylate ester Substitution H TsCI 9T8 cc gt cc I I Pyridine I I Elimination 2 Reactions of Alcohols with HX There are serious limitations on the Use of Hydrohalic Acids with Alcohols 3 Reactions of Alcohols with Phosphorus Halides 3 ROH PCl3 gt3 RCl POH3 3 ROH PBr3 quotgt3 RBr POH3 Mechanism ROH PC15 gt RCl POCl3 Hcl 4 Thionyl chloride SOClz Hquot H i L I SOZCI f gt Note retention of configuration 5 Dehydration Reactions of Alcohols OH Conc H2804 bp161 C bp 83 C show mechanism Review ofOrgam39c I Chem 3331 46 6 The Pinacol Rearrangement 039 C H i 9H3 CHgqchCHg CHs C CrCHs H20 CH3 CH3 CH3 Pinacol make this Pinacolone SHOW DETAILED MECHANISM 7 Periodic acid cleavage of glycols 8 Esteri cation of Alcohols 9 Formation and Reactions of Alkoxides Chapter 12 Stucture Determination IR and Mass Spectroscopy CH3CH2CHCH2 HBr gt CH3CH2CHBrCH3 or CH3CH2CH2CH2Br Once you separate these how do you tell which is which 1 Infrared Spectroscopy Electromagnetic Spectrum g 121 Frequency D Hz 101 1012 1o16 1018 1020 Radio I I I I I I Waves MlCFOW Ves UV Xrays yrays 3 rays 1 102 39 106 108 1010 ViSlbIe Wavelength 7 cm Energy gt Let39s consider the relationship between energy and wavelength Review ofOrgam39c I Chem 3331 47 m Detector solvent l gt lt Electrometer IR I substracts source I solvent ll Recorder Shows IR light absorped by sample as a function of A 4000 frequency cm l 400 100 transmission of IR light 0 2 5 25 wavelength microns 1 p 10394 1 2 3 4 5 Fingerprint aromatic CH o H 00 C0 region C39H N H stretch amp amp reglon CiN Clt StretCh stretch 4000 2800 f 1760 1500 800 Z 00 22602100 Table summarizes the absorption bands for the important functional groups do not memorize 2 Mass spectroscopy Bombard sample with high energy electrons 70 eV A valence electron is knocked out producing a cation radical ee RH 4 RH e6 cation radical Review ofOrgam39c I Chem 3331 48 These cation radicals are passed through a magnetic field which de ects them according to their me ratio De ected particles are detected and recorded by intensity Base peak biggest peak assign intensity 100 Parent peak 2 molecular ion M generally the highest major me value sometimes not observed Two useful type of information 1 Molecular weight just look for molecular ion should be highest me peak sometimes see Ml for isotopes containing 13C can get very accurate MW s 2 Fragmentation Let s consider the case of nhexane CH3CHZCH2CH2CHZCH3 hexane MW 86 e6 CHscHZCHZCHZCHZCHs molecular ion mz 86 I CHsCHchchchz CH30H20H20H2 CH30H2CH2 CH3CH2 mz 71 57 43 29 rel 10 100 75 40 intens Chapter 13 Nuclear Magnetic Resonance Spectroscopy NMR The nuclei of atoms having an odd atomic number or atomic mass 1H 13C 19F 31F 15N etc possess a nuclear spin and can be observed by an nmr spectrometer These nuclei may be considered as spinning about an aXis since they are positively charged these spinning nuclei behave like tiny magnets and thus can interact with an externally applied magnetic field Ho Review ofOrgam39c I Chem 3331 49 A spinning nucleus generates an induced magnetic field H which causes the nucleus to behave like a small bar magnet Let s see what happens when we put a nucleus in an external magnetic field Outside applied magnetic In presence of Ho spins field nuclear spins are align with or against direction randomly oriented of Ho egg cl a bl lt1gt 24gt lower E higher E This behavior is observed for 1H and 13C not 2D or 12C and all nuclei with odd numbered masses The strength of Hg for 60 MHZ machine is typically 14100 gauss If the oriented nuclei in H0 are irradiated with radio waves of the proper frequency energy absorption occurs and the lower energy state quotspin ipsquot to higher E state When this occurs we say the nucleus is in resonance f To bring 1H into resonance H 2 E W 2 E 60 MHz 1000000 cps 0 l For13C i 2 E15 MHZ Review ofOrganic I Chem 3331 50 In practice we hold the RF field constant 60 MHZ and vary the field strength At 60 MHz 14100 Gauss for quotnakedquot H low field H gt high field Nuclei are not quotnakedquot They are clothed by electrons which shield them somewhat from the applied magnetic field Ho In order for us to observe resonance of these shielded nuclei we must apply a magnetic field stronger than H0 Thus different nuclei in different environments quotseequot different effective field strengths and resonate at different values of H0 ie H H ethyl alcohol 3 different kinds of protons H C C O H 3 signals in NMR book uses 0 H3C lt ioCH3 low H gt high H H same is true for 13C spectrum 2 2 peaks Measure chemical shifts relative to tetramethylsilane TMS 1H NMR proton NMR Four important features 1 Number of signals each nonequivalent 1H can give rise to separate peak 2 Chemical shift position of peak gives us some idea about chemical environment amount of shielding of a given nucleus 3 Integration the intensity of a signal tells how many nuclei associated with a specific signal 4 Spinspin Splitting provides information about neighboring magnetic nuclei Review ofOrgam39c I Chem 3331 51 1 Number of signals CH3 CH3 CH30H2OH H 3 signals CH3 C CH3 HC cH CH3 CH3 one signal CH3 H H 2 signals 4 signals H CH3 CH3 H 2 Chemical Shifts shielding effects electron donating move resonance to higher field gt deshielding electron withdrawing move to lower field lt CHC13 73 ppm singlet CH2C12 53 quot quot CH3C1 3 0 quot quot 3 Intensities of Signals Integration 4 Spinspin Splitting CHzBr CHZBrCHBrZ CHBr2 Z 52 r CCCCCCCCCCCC Br csH Br2 NM I I I I 4 3 2 1 0 Equivalent nuclei do not split one another Review ofOrgam39c I Chem 3331 53 The amount of splitting is called the coupling constant and is given in Hz Typical Coupling Constants Approx J Approx J H H H 7Hz 3H2 H 15 lIIi IQ Stereochemical nonequivalence of protons H H2X E Nonequivalent i H diastereotopic gt H 2 g i Five nonequiv protons Time dependent NMR H1 H2 39 rm eq H2 ax Exchange is too fast to see at room temp At 89 C we can see nonequivalent H39s Fast proton exchange If we exchange an H by a D the proton signal will become inVisible by NlVlR We can also use this trick to simplify NlVlR spectra ROH D20 lt gt ROD DOH RNH2 D20 lt gt RND2 2D OH Review ofOrganic I Chem 3331 54 C13 NMR At first it is surprising that we can do 13C nmr on natural abundance carbon which is 99 12C FourierTransform FT NlVlR When we have a weak signal as for C1 3 we can enhance the value of the signal by taking many spectra and adding them together The signals will enhance each other and the noise should cancel out This can be very time consuming Spectral informaton can be obtained in a very short pulse of the Rf field This pulse called a free induction decay FID can be deconvoluted by a computer FT analysis and the spectra or transients added up A Cl3 spectrum typicaly will use from 200500 pulses depending on concentration Proton noise decoupled mode gives one peak for each nonequivalent carbon Normal range of chemical shifts is from 0200 ppm Figure 1240 p 570 summarize the values for different carbons The size of peaks area under them is not normally proportional to the number of carbons responsible for that peak This is not generally a problem and can if needed be avoided by using a gated decoupling mode requires more time between pulses C3 9 CH3CHZCCH3 4 3 21 C2 LI 200 40 Spinspin splitting In the off resonance decoupling mode The magnetic field experienced by 13C nuclei is affected by attached atoms 1H13C which can also induce small magnetic fields Review ofOrgam39c I Chem 3331 55 Chances for two adjacent 13C is very small 01 X 01 110000 quot quot quot adjacent 1H is excellent Thus protons attached to 13C can augment or decrease the effective field a Consider the situation for spin aligned against Ho causes resonance to occur Position of at higher field i signal without Ho effect of H spin aligned with HD causes V resonance to occur at lower eld Hence in the offresonance mode of the spectrometer we observe the CH coupled spectrum doublet coupling constant HZ Jill triplet b Consider CH2 2 1 Review ofOrgam39c I Chem 3331 56 0 Consider CH3 4quot l Thus the off resonance eXpt tells how many H s bonded to C Interpreting 13C NMR Spectra This is quite similar to 1H NlVlR 1 Number of signals tells number of nonequivalent C 2 Chemical shift tells about electronic environment of carbon 3 Peak area not to important 4 Splitting tells about number of attached H s WORK SAMPLE PROBLEMS INWADE


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