ORGANIC CHEMISTRY Alkanes Alkenes Alkynes Ring Structures Cyclic Functional Groups Chain Structures Branches – Substituents

TERMS ORGANIC CHEMISTRY carbon containing molecules HYDROCARBONS carbon & hydrogen molecules

BONDING PATTERNS/REQUIREMENTS Hydrogen (1) Nitrogen (3) Oxygen (2) Halogens (1) carbon (4) X = F, Cl, Br, I N .. : O .. C H X .. : N + Nitrogen Ion, N+, (4)

ORGANIC NOMENCLATURE “Carbon to Carbon” -- bond identification alkANE Single bond between all carbon atoms pg 131 Fromula: CnH2n+2 alkENE Double bond (at least 1) between carbon atoms Formula: CnH2n alkYNE Triple bond (at least 1) between carbon atoms Formula: CnH2n-2

# C’s - ane - ene - yne 1 Methane ---- 2 Ethane Ethene Ethyne 3 Propane Propene Propyne 4 Butane Butene Butyne 5 Pentane Pentene Pentyne 6 Hexane Hexene Hexyne 7 Heptane Heptene Heptyne 8 Octane Octene Octyne 9 Nonane Nonene Nonyne 10 Decane Decene Decyne If structure is a substituent (branch) “yl” ending: methyl; butyl; hexyl

DRAWINGS Skeletal Condensed Line CH3 CH3CHCH3 Structural C H C C C H H H H C C C C

BASIC NAME PATTERN PREFIX --- PARENT -- SUFFIX # of substituent Chain molecules PREFIX --- PARENT -- SUFFIX substituent # of carbons Family - ane - ene - yne

ORGANIC CHEMISTRY name ending single bond: -ane double bond: -ene triple bond: -yne branch (substituent): -yl R, R group: carbon chain # C single bond double bond triple bond 1 methane 2 ethane ethene ethyne 3 propane propene propyne 4 butane butene butyne 5 & more, use prefix for number (5, pent-; 6, hex-; 7, hept-; etc)

NAMING HYDROCARBONS 1. Find longest continuous carbon chain -- Parent 2. Count from end closest to 1st branch -- Prefix 3. Family, base bond type -- Suffix Prefix - Parent - Suffix “-” dashes bet. # & name “,” comma bet. numbers & name

1 2 3 4 5 branch methyl 1 2 3 4 5 branch methyl off of C#4 Parent: 5 C’s, pent Family: single bonds, Suffix; -ane off of C#2 Prefix: branch, C#2 1C: methyl 2-Methylpentane

1 2 3 4 5 6 7 Name: 5 1 2 3 4 =: double bond, functional group, needs to be named & identified where Name:

Name: Name:

If same branch occurs more than once in same molecule; use 2-di, 3-tri, 4-tetra, etc. name:

If same branch occurs more than once in same molecule; use 2-di, 3-tri, 4-tetra, etc. 2 | CH3 name:

O H 2 | CH3 Name:

O 2 | CH3 Name:

O HO Name:

Name: OH Name: Name: OH

.. .. .. . . . . .. .. FUNCTIONAL GROUPS -ane -ene -yne Aromatic Benzene Ring: Arene 6 carbon ring w/ alt. dbl. bonds Alcohol Ether Amine CARBONYL; C=O Aldehyde Ester Amide R CH2 N .. .. R CH2 O H R CH2 O CH2 R .. ending: -ol ether -amine -al -oate -amide R C H O . . R C C O C R O .. . . R C C NH2 .. O . .

Ketone Carboxcylic Acid R C C OH .. O . . R CH2 C CH2 R O . . ending: -one -oic acid RINGS single bonds Multiple bonds Name: cyclo-parent cyclopentane cyclopentene cyclopentyne

FUNCTIONAL GROUP SERIES - OH - O - H - C = O C = O - COOH - COO - Ethers Esters Ketones Carboxcyclic Acids Alcohols Aldehydes

A B C Identify functional group present in each molecule displayed 1: Carboxcyclic Acid 2: Ester 3: Alcohol 4: Carbonyl - Ketone 5: Carbonyl - Aldehyde A H H H C C = O H B O C C C C O C C O C

D E F 1: Carboxcyclic Acid 2: Ester 3: Alcohol 4: Carbonyl - Ketone 5: Carbonyl - Aldehyde D CH3 CH CH3 OH E O C C C OH F O C C C H

G H 1: Carboxcyclic Acid 2: Ester 3: Alcohol 4: Carbonyl - Ketone 5: Carbonyl - Aldehyde G O CH3 C CH2 CH3 H O C C C O C OH

FTIR -- InfraRed IR 1. Bet vis & microwave 2. Organic chemists use 4000 - 400 cm-1 3. cm-1  E of vibration No 2 cmpds give exact sample IR (enantimoers) 2 types of molecular vibration stretching bending 3 vibrations symmetrical asymmetrical scrissoring

Stretching Frequencies () C-C C-O C-N 1300 - 1500 cm-1 C=C C=O C=N N=O 1900 - 1500 C C C N 2300 - 2000 C-H O-H N-H 3800 - 2700 2 imprt areas for prelim exam of spectra 4000 - 1300 900 - 650 1300 - 900 fct group region fingerprint complex Imprt for -OH NH C=O strong bands 1600 - 1310 aromatics (benzene ring) 900 - 650 strong out-of-plane bending & ring bending

C - H Stretch Alkanes 3000 - 2840(s) other: near 1375 & 1450 Cycloalkanes 3100 - 2990(m) other: near 1450(m) Alkenes above 3000(s) other: near 1416(m); 1000-650(w); near 850(s) Alkynes 3333 - 3267(n,s) stronger-narrower than OH & NH other: 700-610(b,s); 1370-1220(w,o) Aromatics 3100 - 3000 & 2000 - 1650(w,o) other: 900-675(s); 1300-1000(m) Aldehydes 2830 - 2695(2:s) w/ near 1390 other: near 2720(m)

C to C Alkanes below 500; 1200 - 800(w) are of little value best is C-H CH3 2962 & 2872 CH2 near 2926 & near 2853 (+/-10) CH near 1375 & near 1450 Alkenes 1667 - 1640(m) Alkynes 2260 - 2100(w)

ALCOHOLS -- PHENOLS ETHERS Alkenes - Phenols -OH & C-O OH 3650 - 3584(b,s); 1420 - 1330(m) CO 1260 - 1000(s) Ethers C-O-C similar to C-C-C but more intense 1150 - 1085(s) ETHERS Ethers C-O-C similar to C-C-C but more intense 1150 - 1085(s)

CARBONYL C=O containing Carbonyls (ketones, aldehydes, carboxylic acids, esters, anhydrides, amides) C=O 1870 - 1540(s) Ketones 1300 - 1100(m) Aldehydes 1740 - 1720 C-H 2830-2695(2:m) & near 2720(m) Carboxylic Acids O-H 3300 - 2500(b,s) C=O near 1766(s) C-O & O-H near 1320-1210(m) & near 1440-1395(m) Esters C=O 1750 - 1715(s) higher freq than ketones C-O 1210- 1163(2:s)

NITROGEN CONTAINING Amides NH2 or NH 1650 - 1515 other: near 3520(m) & near 3400(m) C=O 1694 & 1650(s) C-N near 1400(m) Amine NH near 3500(w) & near 3400(w) other: NH 1650-1580(m) C-N 1250 - 1020(m) aromatic C-N 1342-1266(s) Nitriles CN 2260 - 2222(m) Discuss Galvani & Volta 31

SUMMARY Alkanes, alkyl groups C-H 2850 – 2960 m – s Alkenes =C-H 3020 – 3100 m C=C 1640 – 1680 m Alkynes C-H 3300 s -CC- 2100 – 2260 m Alcohols O-H 3400 – 3650 s,b C-O 1050 – 1150 s Aromatics =C-H 3030 m ring 1600, 1500 s Amines N-H 3300 – 3500 m C-N 1030, 1230 m Carbonyl Cmpds C=O 1680 – 1750 s,b Carboxylic Acids O-H 2500 – 3100 s,b Nitriles CN 2210 – 2260 m Nitro NO2 1540 s SUMMARY spontaneous rxn = -G this is a mathematic eqn have discussed conditions that make G +/- -G(exo) when -H(exo) & +S 32

N-H O-H C-H CN CC C=O C=N C=C Fingerprint Region % Transmittance 4000 3000 2000 1600 1200 1000 800 600 (cm-1) % Transmittance N-H O-H C-H CN CC C=O C=N C=C Fingerprint Region

ALKENE % Transmittance 4000 3000 2000 1600 1200 1000 800 600 (cm-1) 4000 3000 2000 1600 1200 1000 800 600 (cm-1) % Transmittance Discuss Galvani & Volta 34

ALKYNE % Transmittance 4000 3000 2000 1600 1200 1000 800 600 (cm-1) 4000 3000 2000 1600 1200 1000 800 600 (cm-1) % Transmittance Discuss Galvani & Volta 35

ALCOHOL % Transmittance 4000 3000 2000 1600 1200 1000 800 600 (cm-1) 4000 3000 2000 1600 1200 1000 800 600 (cm-1) % Transmittance Discuss Galvani & Volta 36

Website for spectral information of molecules http://riodb01.ibase.aist.go.jp/sdbs/cgi-bin/cre_index.cgi?lang=eng