Organic Chemistry Subnote

, 9 line structure, condensed structure 9 octet rule 9 : , , ()- 9 =resonance energy

, , , , carbon , chemical bond Hybridization of carbon 2 Nomenclature Trivial name, Geneva common name IUPAC Haloalkylalkane bromomethan Derivatives name : methyl bromide C-Br Alkane homologous series chemical reaction 9 combustion : O2,spark, 9 cracking : , 9 halogenation : radical

Stereochemistry Structural isomers Geometrical isomers

Conformation of open-chain : newman, sawhorse 9 eclipsed conformation, staggered conformation 9 anti, gauche

Conformation of cyclic compound 9 boat 9 chair

A work of uwilmsme do not copy or distribute / admit.woweb.net

-

: : ex)

cis,trans 9 (enantiomers) - , 9 (diastereomers)

stereocenter

DNA

R-S Cahn-Ingold-Prelog ( )

(b.p, m,p) , , IR, ( )

[ ] = / ( g.mL-1 * in dm=10 cm) R,S (+,-) meso compounds

. Fisher (Prochirality)

(+1) (0) (-1)

E1, E2 reaction E1 reaction

9 Carbocation 9

E2 reaction

9 OH- RO- 9 9 1 < 2 < 3 (as E1)

Saytzeff rule : ( ) 9 Anti-elimination 9 Cyclohexane ( 2003. 24)

Hofmann product : (Steric hindrance) 9 9 9

SN E

i. ii. iii. iv. v.

1 Inductive effect

2 Hyper Conjugation

9 Br- Cl- ROH H2O() CN- OH- RO-() 9 -

9 H2O ROH Cl- Br- OH- RO- I- CN- 9 9 9 ( )

DMF, DMSO

:

Gridnard Oxirane Oxirane

: 1 : 2 : 3 + 2 Gridnard : 3

-OH, -NH2, - CO2H, -SO3H, -SH -OCH, -OCR, -COOR, - CONH2, -NO2, oxirane

R2CuLi + RX R-R ArX, ! Nitrile 1) Grignard 2)

Alcohol Structure sp3

Physical properties

b.p, m.p, (acidity) : phenol(,pKa=10) > MeOH > H2O(pKa=15.74) > 1 > 2 > 3 ( ) : RO- (alkoxide ion) : oxonium ion alkene : 9 9 Markovnikov : carbocation + Ex) 3,3-Dimethyl-1-butene ?

- : anti-Markovnikov Oxymercuration-demercuration : Markovnikov. Hg(OAc)2+OH-+NaBH4 9 (1) NaBH4, LiAlH4(LAH) 9 (2) H+, H2O

RX + OH- -> ROH (1) Grignard(RMgX) 9 9 9 RLi : steric hindrance 9 ,,,epoxide,ester

) Mg diethyl ether , , HCl . ?

Substitution ROH+HX -> RX

9 SN2, SN1(, ZnCl2 ) OH H+

9 1 < 2 < 3 , HI > HBr > HCl (HF ) 9 2, 3, ,

ROH+PBr3 or PCl3 or SOCl2(w/ R3N) -> RX : SN2 Esterification 9 ROH+RCOOH -> RCOOR 9 H+,heat

, : Ts, Ms ( Esterification)

1) ROH+TsCl or MsCl (w/)-> RO-Ts or RO-Ms : 2) SN2 (tosylate leaving group) :

Elimination 9 c. H2SO4 9 1 < 2 < 3 (E2, E1) 9 ex) 2,3-dimethyl-3pentanol 9 benzyl ex) 1-phenyl-2butenol

Ether 9 2ROH (w/ H+)-> R-O-R 9 Williamson : RO- + R-L(X) -> RO-R

Oxidation

PCC, KMnO4, K2Cr2O7 3--3- . ?

(CH3)2C=CHCH3

1) ROH + 2) ROH + TBDMSCl (tert-Butylchlorodimetylsilane)

A work of uwilmsme do not copy or distribute / admit.woweb.net

Ether, epoxide Ether Nomenclature

Common name : ~ ether, IUPAC : alkoxy- 1 : alkene(), ether()

Williamson ether : SN2 , SN2 - Solomon) 11.16,17 Crown ether Epoxide Nomenclature

Common name : epoxy-, IUPAC : oxirane 9 alkene+ in (CCl4) 9 1,2-halohydrin : Williamson

: () (SN2) : / Grignard : Thiol Nomenclature

Thiol/mercaptan : -SH thiol group, sulfhydryl group

H2O,ROH : b.p

Reactions

HS- + RX -> RSH (->RS-) RX + RS- -> RSR (sulfide, R2S) Thiol(RSH) I2, K3Fe(CN)6 disulfide (RSH -> RS-SR) R2S -> sulfoxide(H2O2,125), sulfone(H2O2,100) 9 KMnO4, K2CrO7

DMSO Chiral . ( , )

Alkene and Alkyne 9 trans > cis 9

- R sp2 : 9 1 : E2

(tert-butoxy ion), , 9 2 : ROH (E1) , RX E2 9 3 : ROH E1, RX E2

Oxymercuration-demercuration

9 Hg(OAc)2+OH-+NaBH4 9 9 Markovnikov

Hydroboration [ -] BH3 + alkene -> R3B 9 H : -> anti-Markovnikov cf) 9 H2O2, OH- : alcohol 9 Syn addition, 9 + : - (Solomon P.424)

Halogen 9 CCl4 9 alkene 9 -> ( )->anti 9 Halohydrin : ( , ) - (-OH)

Carbene(R2C:) 9 Cyclopropane 9 (Simmons-Smith ) : ICH2ZnI Zn(Cu)+CH2I2 9 CCl2 : CHCl3 + (CH3)3O-K+

() (H2SO4,HgSO4) : , (),

Alkene Sigma bond : epoxide, diol 9 cold KMnO4 + OH- +H2O = OsO4+Na2SO3/H2O : syn hydroxyl - cis 9 Baeyer : . KMnO4 -MnO2 9 Epoxide : , CH2Cl2 . H2O,OH- (SN2) trans-diol 9 O2, PdCl2 /CuCl2 : methyl ketone

Sigma bond : ketone, aldehyde, 9 hot KMnO4 + OH- +H2O : (ketone+), CO2 : O3 ozonide 9 (Zn/AcOH or CH3SCH3) 9 (H2O2)

Alkyne sp -> -> -> /

RCCH + NaNH2 / Grignard -> RCC- (acetylide ion)

9 Pt/H2 : alkane 9 P-2 catalyst(Ni2B), Lindlar(Pd) : syn alkene 9 (Na or Li) + NH3 or C2H5NH2 : anti

9 Cl2,Br2 : anti 9 HX : Markovnikov 9 *) anti- Markovnikov radical HBr

Alkyne O3 + AcOH / KMnO4 + OH- + H+ CC ()

Conjugation Pi Bond ( ) C2-C3 , 1,4- 9 1,2- 1,4- ( : 1,4) 9 1,4- : (polyisoprene), neoprene

Diels-Alder s-cis , syn () : endo( trans : ), exo

, - 1,4- 1) 1-4 : H+ , , 1,4- 2) 1,4- H+ (1,2- or 1,4-)

(RMgX, LHA) C=C (R2CuLi) : 1,4-

3) , - conjugation 1,4-

Spectroscopy IR(InfraRed Spectroscopy)

( E ) (fingerprint region) C=C 1600-1700 cm-1, C=O : 1640~1820 cm-1

CC 2100-2250 cm-1 CN 2200-2300 cm-1 OH, NH : 3000-3700 cm-1 C-O stretching(ester) : 1100-1300 cm-1

NMR(Nuclear Magnetic Resonance)

+ : parallel, aniparallel ->(,), 9 downfield : deshilded, upfield : shielded 9 : 9 : n+1

C13 NMR - () . : . 2.3 : 7 CHO : 10, COOH : 11 Mass spectrometry

E +

m/e : base peak 100% ( ) : n-> -> McLafferty : UV-Vis

(, ) , , n

NMR

Ar external field deshielded lower field proton peak ( ) lower field proton spin-spin splitting N+1 Rule

aromatic proton . proton (equivalent) splitting multiplet splitting proton (upward)

Peak 2.1-2.5 : carbonyl group, sharp 2.5 : terminal alkyne 3-4 : electronegative element carbon 5-6 : vinyl proton 7-8 : aromatic ring, 7.2 : electron-withrawing substituent 9-10 : aldehyde acid OH() : past 10 ppm

A work of uwilmsme do not copy or distribute / admit.woweb.net

Glycols 1,2-diol = glycol dehydration of pinacol

dehydration rearrangement : charge (-OH) ketone ex) Fessenden P.330 7.54 oxidation

periodic acid(HIO4) glycol carbonyl group cyclic periodic ester Additional Sections for Alkynes Oxymercuration-demercuration : Markovnikov Hydroboration [ -] BH3 + alkene -> R3B 9 H : -> anti-Markovnikov 9 H2O2, OH- : alcohol 9 Syn addition,

For Alkynes

1) Alkyne(RR) -> BH3 -> trialkenylborane -> RCOOH -> boron H (alkene) 2) Terminal alkynes(RCH) : 9 Sterically hindered disubstituted borane[(sia)2BH] : single addition (alkenyl borane ) 9 H2O2, OH- : enol -> ketone (isomerism : keto-enol tautomerism) 9 . Alpha

Electrophilic Addtions Br2 and Cl2 - anti addition

Addition of HX

9 Markovnikovs rule 9 Vinylic carbocation is unstable -> alkynes are less reactive

*) PVC using vinyl chloride (free radical reaction) Hydration

Using H2SO4,HgSO4 results enol->ketone Organic Synthesis : retrosynthesis

: : :

9 I2 < Br2 < Cl2 < F2 9 Ea

: racemic(sp2) racemic : : 9 Br2 () vs Cl2 9 Hammond

NBS

NBS+HBr : Br2 () Br2+ or : () Anti-Markovnikov HBr (HCl ) Br anti pi Polymer

( ) Poly ethylene(ethylene), Poly stylene, poly(vinyl chloride= PVC), polytetrafluoroethene = Teflon : Vitamin C,E Freon

1. CF2Cl2 CF2Cl. + Cl. 2. Cl. + O3 ClO. + O2

anti-hydroxyl

epoxide + H2O syn-hydroxyl

cold KMnO4 + OH- +H2O = OsO4+Na2SO3/H2O - cis syn BH3 + H2O2, OH- : alcohol H2 + Ni Diels-alder Anti-Markovnikov Hydroboration Reactions with peroxide (radical reaction) Polymers ( )

: (ROOR) : () : Poly ethylene(ethylene), Poly stylene, poly(vinyl chloride)= PVC, polytetrafluoroethene = Teflon Poly(methyl methacrylate)

Polyaminde

, (isocyanate+phenol), Kevlar Poly ether

Poly ester() - Ester+alcohol 1,4-()

( CH2=CCH3-CH=CH2 ), neoprene, poly(ethylene terephthalate)

m-chloroperbenzoic acid (C7H5ClO3)

(Phthalic acid)

dicarboxylic acid 2C Oxalic acid 3C Malonic acid 4C Succinic acid trans-2-chlorocyclohexanol, cis-2-chlorocyclohexanol + NaOH ? solomon 11.22

CO2H

CO2H

ckeluH && 9 9 4n+2 9 : Pyridine vs Pyrrole

. : X2 / FeX3 : HNO3/H2SO4 Friedel Craft : RX+AlX3 Friedel Craft : RCOX+AlX3 : SO3/H2SO4

, (o,p- /m-) : +

9 9 9 9 Kolbe : +CO2 salicylic acid 9 Reimer-Tiemann : +CHCl3 salicylaldehyde

9 Fe/HCl OH- 9 NaNO2,HCl at 273K (PhN2+Cl-) CuCl, CuBr, KCN KI, HBF4 -OH H : H3PO2

. SN2 , SN1 - (sp2, )

-

(NO2 ) o-, p-

-

( or NH2- ) Benzyne

Aldehydes and Ketones : C=O , ,, C=O : 1730(CHO),1715 cm-1 ( ) 1H NMR : 9~10 ppm, 13C : 200

1) 9 : CrO3 , PCC 9 : DIBAL-H + ester or nitrile / LiAlH[OC(CH3)3]3

2) 9 , (-) 9 +R2CuLi, (Friedel-Crafts) 9 nitrile - Grignard

: , . ( ) : gem-diol : hemiacetalacetal 9 9 () 9

ex) 1) HOCH2CH2OH + HA 2) H+ Q HCN : cyanohydrin, CN- Grignard : ROH Reformatsky Solomon 9 aldehyde or ketone + Br-C-CO2R (Zn) BrZnO-C-C-CO2R (H+) HO-C-C-CO2R 9 ester ()

- NH3 (RNH2) 9 Imine (C=N group) : RCHO+RNH2 -> RCHOH-NHR (-H2O)-> RCH=NR

(R2NH) 9 enamine

(H2N-OH) 9 (C=N-OH)

Hydrazine 9 :

: Wittig 9

9 4 , 9

9 9 LAH : , , , ester 9 NaBH4 : , ester ( ) 9 DIBAL-H : *) 9 Camphor LAH , OH

Wolff-Kishner/Clemensen ( ) Wolff-Kishner : , 1) 2) OH- Clemmensen : , Zn(Hg) / HCl Friedel-Crafts : , Raney Ni

1) NH3 2) H2,Ni

( . ) 9 KMnO4 or Ag2O, OH-/H+

Tollens : - Ag(NH3)2+/H2O Baeyer-Villiger : 9 : H>Ph>3>2>1>Me Solomon

: ,

- :

/ : /

CHX3 -> :

- OH , C=O : 1700 cm-1 NMR : 13~19 ppm, - 2.2 ppm

, (KMnO4, O3/H2O2) Grignard + CO2 ()

(Ar-,COO-) : .

+ 9 9 ate

9 +ROH 9 : (3

() Acyl group or Nitrile group . ( ) cf) , :

ester : +, +, +, + : ester : : 9 , () 9 ester : ester+alcohol 9 : ester + 9 : , LAH 2 9 Grignard : 3 (OR ketone )

: , - ,

: + / () spectrum : ,, : C=O -> CH2 by LAH. NaBH4 : : , (isocyanate+phenol) : CN- (RX-1 , ), 9 (,) : (NH4+ or NH3 ) 9 Grignard

: , LAH (CH2NH2) 02-15, 01-4,15, 00-1-2, 98-4

Enolate , enolate OH 9 (NH2-,H-) 9

Nitroalkane,Nitrile :

: : RX SN2, 2

1,2 LDA(Lithum DiisopropylAmide)

9 9 Diisopropylamine + RLi = LDA

( ) . :

9 .

, :

: +2(13.5B) : SN2

9 2 9 9 9 ( , ) ( )

conjugation Knoevenagel : : Thioester

: (,) Claisen : Ester+Ester

: ester ester , ROH :

Dieckmann = Claisen (5,6 ) Claisen : Ester , aldehyde ketone 9 Michael 9 + 9 (RCu,R2CuLi) 9 Robinson = Michel +

- LDA, PhSeBr , PhSe . solomon P.681 H2O2 : , 98-27,99-4.3,02-13,00-7,01-9

A work of uwilmsme do not copy or distribute / admit.woweb.net

sp3, . IR : OH 3300 peak NMR : HN . 2.2~2.8 ppm(N ) : , , sp2>sp3, ( ), 9 : RX+NH3 (SN2) (4 ) 9 , 9 Gabriel : SN2 /, 1

: Hofmann 9 + OH- + Br2 + CO32- + 2Br- 9 +Br- RN=C=O :

: : ,, + 9 + () 9 + = : Hinsberg Test

1 : , 2 : , 3 : 9 amine + aldehyde/ketone = ,

: 0 , : , Hofmann 4 : 4 +Ag2O 4 R3N+ : 1

Cope 3

00-2/1, 01-1/9, 02-13 b)

N

II : 1 9 9 (V2O5) : 9 (,Na,EtOH) 9 : , 1 ( )

( sp2 ) : Pyridine vs Pyrrole

1, 6- 9 : , 3 9 (SNAr) : 2

: Friedel-Crafts sp2 ( ) : : (2 , ), -

: < <

: < 2- (~) 1 : (5,8 ) : (1 or 2 ) , heme, cytochrome(Fe2+), chlorophyll(Mg2+) Cu2+, ,

2 (phenylalanine hydroxylase) PKU Purine, Pyrimidine, NAD+( ) : , G , (3/4 )240 (CoQ), K

HOMO : Highest Occupied Molecular Orbital LUMO : Lowest Unoccupied Molecular Orbital 9 [2+2] : 9 Diels-Alder : [4+2] ( )

9 conjugation 2 9 [4n] : ( ) hv( ), () 9 [4n+2] : [4n]

9 , , 9 Claisen : Ally Phenyl Ether o-Allylphenol / allyl vinyl ether 9 Cope

Friedel-Crafts (3-Benzoylpropanoic acidZn(Hg)/HClSOCl2AlCl3) h D 9 9 , .

monosaccharide-disaccharide-oligosaccharide-polysaccharide monosaccharide

aldose : aldehyde glucose,galactose,ribose ketose : ketone fructose hexose : 6 (tri-,tetr-) aldohexose, aldopentose : 2^() ,,,(+) glucose : dextrose() fructose : , . Sucrose glucose fructose ribose,deoxyribose : pentose epimer : ex) glucose & galactose D,L : OH D : Hemiacetal : 5 : 6 Haworth : D , 9 1 9 -(,trans) : , -(,cis) :

: Tollens aldose, fructose () polysaccharide :

, , () : , , , : micelle

L : , -NH3+ pKa, -COO- pKb : ()() : pH Cys

C Chain Ser OH

C Chain Thr OH,* + Thy OH,Phenyl Acidic

S Asn Amide Asp Phenyl Gln Amide Glu OH Phenyl Basic

C Chain Gly H Lys *Ala C ArgLeu * C Chain HisIle * C ChainMet * SCH3Phe * PhenylTrp * PhenylVal * C ChainCys SHPro Ring

DeoxyriboNucleic Acid, RiboNucleic Acid Nucleotide : ++ Nucleoside : + : AG, : CTU DNA

20A, 34A : pH, , : B-,A-,Z- B-DNA : Watson-Crick B-, DNA , A-DNA : Z-DNA : ,

: 5->3 RNA

tRNA 9 3 -CCA 9 anticodon arm, D arm, arm(),

Rna Pol. I : rRNA, II : mRNA,snRNA, III : tRNA, rRNA(5S)

(Mutarotation) ()

D- - : C1 OH , -D- 2002

2000-1

(2) 730-770,690-710 cm-1 o- (1) 735-770 cm-1 m- (3) 869-900,750-810,680-725 cm-1 p- (1) 800-860 cm-1

*) m- 2 peak

2003

() 2001

2002

99

02

02

01

, pKa=10

(R )

3 o >2 o >1 o >NH3 () 3 2,1 . 3 (CH3)3NH+ 1 .

2 o >1 o >3 o >NH3 () + (negative) 4 4

: hydronium ion : oxonium ion alkoxide ion RO- > OH- - (NaH, KH)

H2O > CH3OH > CH3CH2OH

HCl (water-immiscible solvent) CH2Cl2 ether

1) hexylaminium chloride + NaOH hexylamine ether

2) NaOH , sodium bicarbonate , 3) ( ) NaOH

(distillation) 2004, 2004

A work of uwilmsme do not copy or distribute / admit.woweb.net