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Fund of Organic Chemistry II

by: Dominic Kling

Fund of Organic Chemistry II CHEM 3332

Marketplace > University of Houston > Chemistry > CHEM 3332 > Fund of Organic Chemistry II
Dominic Kling
GPA 3.71

Thomas Albright

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Thomas Albright
Class Notes
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This 32 page Class Notes was uploaded by Dominic Kling on Saturday September 19, 2015. The Class Notes belongs to CHEM 3332 at University of Houston taught by Thomas Albright in Fall. Since its upload, it has received 124 views. For similar materials see /class/208158/chem-3332-university-of-houston in Chemistry at University of Houston.


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Date Created: 09/19/15
Chap Mme A Properties 1 basicity Ammonia acting as a Bransted base in proton transfer Ham H it quot39 HBItI H 31 Ammonia acting as a nuc emphile in an 8N2 reaction u u a HsNt CiIg jf 1quot HSN CH3 I Chapter 19 THE END 1 an competitor for H and produces weak Bronsted acid high pm i i R NH2 H X quot H NH3 x A strongly basic amine is a good ammonium ion that is a relatively A weakly basic amine is a less effective competitor for Hr and produces an ammonium ion that is a relatively strong Bronsted acid low pKa a inductive effects Liking q iliiilii3 lt MHEH2 it NH3H Order oi increasing gzasphase P39Ka Lowest pKa Highest pita Chapter 19 THE END b aromaticity NH3 NH3 MEWS pKa 46 108 0 quot 0 N H N pK 1o I H H H Chapter 19 THE END c hyb dization Et N Et N quotI I c Et I 108 53 CHS 1o pig of NH d amides R Q H B R j H3 Alcohol Aikoxide ion pKa 17 P iiH2 B R NH H8 Amine Amide ion pKa 36 BuLi CHBCHzizNH CHgCH22NZ Li BuH E Amide ion E 2 structures Ni N H quotquot H Hac quotquotquotCHs H quot quot CHs n y l A 39 N Acarbon based pyramid is static B quot Q G C quot N Mirror The nitrogenbased pyramid can invert Planar transition stare sp x R R KR R db N L N NO W amp GQW sp3 hybridization at N pyramidal lt 0 uml inversion produces the mirror image pyramid H Hac N CHSCHg AC1 i 5 kcaUmol One enantiomer H O Q WCH3 CHZCHS CH3 H30 0 H30 Q CH3 Q H3 gtAN gt H30 0 CH3 H30 D H30 0 The barrier to this inversion is unusually high AG 185 kcaLmol HqC 0 H30 Q Ph gtAN gtAN O H30 Ph H30 When the methyl on nitrogen is replaced by phenyi AG decreases to 112 keelmo Chapter 19 THE END The other enantiomer WHY B Nomenclature NHQR NHRE NR3 NR4 NHS Tertiary amine Ammonium ion Ammonia Primaryamine Secondaryamine 1 common name the alkyl portions and follow this by the suffix amine ie CHSN39H2 CHQCHQNH2 PhCHNHD CHSJQNH CH30H23N Methylamine quot Ll39 39 39 quotquot Ll39 39 Triethylamine u NH IZHZCHS IDHZCHQ HNCH3 PhCH2NCH3 CH3SCKIH2 CHGCHZCHZNHZ ltgt NHJ Ethylmethylamine Benzylethyl Mquot 39 r 39 f 39 39 I notmethylethylamine methylamine 2 IUPAC drop e in alkane name add amine Chapter 19 THE END NH fHa CHQ NH CH3CH2CH2CHNHCH3 4 2 M eth an amin e Cycloh exanamin e N39methVquot239Pequottaquotamiquote 3 naming as a substituent amino VN39Hg z 1 lsobutylamine 2Amino3chlorobulane 3 Amino 2butanol W amino2methylpropane not3amino2 chlorobutane or s Amino2 hydroxybmane not 2amino3butan01 or 2 amin073 hydroxybutane gm Hi 3 2 2 3Brom ocyclopentylamine 3Aminocyclopentanol neither 3 aminobromocyclopemane not shydroxycyclopentylamine nor 4bromoaminocyclopemane Chapter 19 THE END 8 4 aromatic amines heterocycles NHZ NH2 NH2 NH2 H 631 CH3 Aniline 39 L39 L IA I 39 In quot m Y 1 39 ptoiuidine 2Q 7 1 N Pyridine Quinoline Isoquinoline Acridine I Z H Carbazole Pyrrole mdme Chapter 19 llib bNL v 0 N N l l l l H H H H Aziridine Azetidine Pyrrolidine Piperidine azacyclopropane azacyclobmane azacyclopentane azacyclohexane 1 9 2 quot13 N 1 l CHgPh N l H not 5me tHylEJiperidine not 4 bron 16pyrrolidine Nbenzylmor39pholine Chapter 19 THE END C Spectroscopy 1 IR 1 amines 2 peaks 2 amines 1 peak 3200 3500 cmquot1 2 1H NMR broad peak for NH 61 4 ppm exchanges With D20 D Uses 70 000 Haber Bosch process N2 H2 gt NHs makes 30 billion tons per year 1000 atm fertilizer CHZCHZCHZCHZ CHZCHZCHZCHZCHZ NH2 NH2 NH2 NH2 putresciene cadaverine oder from decaying esh produced by bacteria You guessed it Chapter 19 THE END 11 Alkaloid any nitrogen containing compound extracted from plants Plant hemlock morphine leOHBO L Q IUCHQCHZCHS H HH Ammonium Ion water soluble lbase 39 u QVICHQCHQCW Codeine Heroin H I H stennime opium alka101ds Chapter 19 THE END 12 NCHS INCH3 NCH 3 5 COOCHG H H 9 H u u C 20 CHeQH 2039 CHng o CClt C Clt o Ph 0 Ph Atropine Scopolamine Cocaine tropane alkaloids 0 II c NH CH3CH22N lndole Ho ElQCHZNH2 CHZCH3NCH32 H202 1 NH Serotonin Lysergic acid diethylamide Psilocin LSD indole alkaloids Chapter 19 THE END 13 bark of the cinchona tree treatment for malaria one Of the first molecules to be synthesized CHGO CHZCHZCHs E10 30 Sildenafil 0 N citric acid salt 0 Viagra Patent t0 Pfizer 192 ampl993 Chapter 19 THE END Bittex most bitter substance lumwn womplewly nontoxic 39 thumb sucking amp ngmail biting D Reactions of amines 1 formation of imines see Chapter 1816 39039 R 39H39 R NH2 H C d luteacid C u H CH3 H CH3 mine Note 0 RNP 39JI39 LN C diluteacid C H H CH3 H cH2 Enamine 0 know reaction mechanism acid and base cat Chapter 19 THE END 16 2 nucleophillic substitution n 5N2 CH133N2 CHg U gt CH33N CH3 l Tetramethylammonium iod idie But 8N2 NHa H3N CHe l gt HsN CHS gt H2NCH3 NH 1 Primaryamine 3N2 CHQNHQ CHaNHg CHg I gt CHSNHg CHG I Z HNCH32 CHSNHa 1 Secondary amine CH3gt2NH lt sNz New CH32NH2 1 CH32NH OHS l gt CH32KlH CH3 1 Tertiaryamine But H3N CH3307 gt HaN CCH33 t 8N2 No 8N2 for teniaw ubstrates Chapter 19 THE END 17 3 elimination reactions oH H 5H0 The major alkene a produced is the 2 akene k lt 39 X H2039 the more substituted Saytzeii product 39 39 NHE CHE I 39 NCH39 AgOH NCHlt3 H Agl cSH l A The major alkene produced is the less substiiuted 1aikene a Hofmann product CH33N H26 4 Aromatic substitution NH2 is a very strong activating group NH3 is a very strong deactivating group An activating orthopara A meta director directing group but deactivating NH2 NH2 Ni i2 NH3 NH3 H2804 HNO HNOS 3 HN03 No 3 NHZ NH2 INH2 Bi To get around this we normally use an amide I39l H C C HN CH3 HN CH3 0 II c 9 CH3 HNO3 NaOH gt gt pyridine H2804 H20 NAcetylaniline acetanilide N02 79 para The remainder is mainly onho Chapter 19 THE END 5 the Sandmeyer reactions NHQ CZJZI N2 NaONOHCI C gt Aniline Benzene diazonium chloride N2 CN N2 Br CuCN CuBr gt 0 CC 5 h water acetone 725 DC CH3 CH3 No2 N02 67 90 Chapter 19 THE END N CI CuCI CH3CN 65 CC c 0 H30 o HC 0 98 20 N OH NZ H3P02 Cu gt gt CueH20 25 OC 1 min CH3 CH3 80 93 N I KI 25 100 50 C gt HBF4 0 gt0 75 N2 F Schiemann reaction 69 Chapter 19 THE END 21 E Preparation of amines 1 reduction of NO2 and CN compounds NEC CH23 CEN NHrCHrCHga CH2 K1112 125 quotC 80 N NH 0 z 1 HAM14000 gt C G 21 1201130 72 1 IT H5O c NiH2 H3O c H C OCHS 1000 psi H C OCHS 3 No2 55 C 3 NH2 mm 92 Chapter 19 THE END 22 39NHZ NOO HZPdC EtOH quotP nitration gt i T Brim gt prep 0f 2 OWH20 diazo compd Nitro Aniline bein zen e Sandmeyer rxns 2 reductive animation M NH NH NH3 C HzNi 140 0C 28 aim An unisolated 99 intermediate Chapter 19 THE END 23 A new reducing agent sodium cyanoborohydride O NHCHS C NaBHCN CH CHS CH3 NH2 Jgt CH3 CH30H 25 CC 95 OH 6H b39H N HN N NH2 NaBHQCN H2 RhC gt gt CHSOH 25 C CH3CH20H Cyclopemanone oxime A hydroxylamine Cyclohexanone oxime Cyclohexylamine 77 55 Chapter 19 THE END 24 3 acylation reduction 390 NHs 390 1 LiAIH4 n c cn gt R C NHZ gt R CHzNHZ pyr or 2 H20 NaOH 390 NR39H2 1 LiAIH4 R c CI gt R C NHR39 gt R CHz NHR39 pyr or 2 H20 NaOH 0 0 I NR2 1 LIAIH4 R c c R C NR39Z gt R CHz NR39Z pyr or 2 H20 NaOH Also 02 0 g H 1 LIAIHJ 0 u 39 eme CHrN anz NH 1 NaH MCHS 35 1 h gt gt 2 CHE 1 21120 twice Chapter 19 THE END 25 an Riffs A he general procedure COOH COOH Phthalic acid Phthallmide COOH H 80 R NH2 M F NH3 2 4 H20 H20 A prlmary amme K200a PhCHQC gt 190 a0 a h 6 reduction of azides 1393 KIT SVZ HqPd c quoton gt u c Ci CHsiscg CHz CHaJsCQ ICHE quot 0 2nKiNr N3 Azide ion 92 7 Hofmann rearrangement H 3quot H Tl H 1 RCN gt RC FKCNB i 39 H i2 L 55 1 Na QH another neighboring migration of R group effect C An isocyanaie but not isolabie under these conditions Chapter 19 THE END 27 0 A 3 H20 protonation gt HC R 9 k H Acarbamic H6 add H HO H decarboxylation protonation Hg H N Z N cog H20 R R Anaminei the end produm of the Hermann rearrangement K C NH2 NHz C12NaOHH20 CO gt 50 5030 U 2 CH3 CHQQ QCHS QCHB 81 i o I N 9 HN C H20 gt QH CHJIQ CH3 390 2 QCH3 An lsocyanate Acarbamic acid 28 Unstable nonisolated intermedlates 8 Curtius rearrangement 0 O 0 Na N3quot in y H g 9 Na 9 1N NEN An acyl azide migration 01R as Ngis lost a neighboring group effect QCN 0 Pl I An Isocyanate CQ7 02 NENZ loss of N3 RON A nitrene Chapter 19 THE END 29 H2quot 1 Cp n H NHE CO 0 R l RQH HCr What happens us1ng Nzczg quot R an amine RNHZ H A carbamate ester Cunius H39 a 4 RSSNUEN gt QCN N2 Isolable No nucleophiles present Bu1Hofmann SO I H B HO m f 70H H20 RCN r R EEBr 920 H20 CO2 Rip RiNHz Notisolable H born in the presence DfOH E Summary 1 Basicity 0f amines 2L inductive effects b resonanaej ammaticity t3 hybridizatim 2 Pyramidaliza on 0f amines 3 Nummlamre 4 Swampy 5x Amma c substimtien a using middesace1a1nidcs b Sandmayer reclaims 6 Reduction mactinns a NO2 and EN h mductive animation ch acylaticm radnctian 7 Gatn39iel synthesis Wmmmm 8 deuc en 6f 321668 9 Hofnmnn management mach 10 Curling rem rangcmant mezzh


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