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In this handout, all of our functional groups are presented as condensed line formulas, 2D and 3D formulas and with nomenclature prefixes and suffixes (if present). Organic names are built on a foundation of , and . Those examples are presented first and you need to know those rules. The strategies can be found in Chapter 4 of our textbook (alkanes: pages 93-98, 102-104, alkenes: pages 104-110, alkynes: pages 112-113 and combinations of all of them 113-115). After introducing examples of alkanes, alkenes, alkynes and combinations of them, the functional groups are presented in order of priority. A few nomenclature examples are provided for each of the functional groups. Examples of the various functional groups are presented on pages 115-135 in the textbook. Two overview pages are on pages 136-137. Some functional groups have a suffix name when they are the highest priority and a prefix name when they are not the highest priority group, and these are added to the skeletal names with identifying numbers and terms (E and Z for alkenes, R and S for chiral centers and cis and trans for rings). Several low priority functional groups only have a prefix name. A few additional special patterns are shown on pages 98-102. The only way to learn this topic is practice (over and over). The best practice approach is to actually write out the names (on an extra piece of paper or on a white board, and then do it again). The same functional groups are used throughout the entire course. Once you know them, it’s like shuffling a deck of cards. The queen of hearts is always the queen of hearts, and an is always an ester. The main variables for a functional group are highest priority (suffix) or lower priority (prefix) and what number identifies it.

Alkanes prefix = none suffix = -ane

alkanes - try to draw 3D structures in a zig-zag shape 2D H H H H H H 3D H H H H C R H C C H 5 3 1 4 2 R C CH3CH2CH2CH2CH3 C C C H C C H C C C H H H H H H H H suffix: #-ane condensed line formula H H H H H H IUPAC: IUPAC: pentane 3-ethyl-2-methylpentane prefix: none alkanes Add 2 to "n" to include the end methyl groups (total chain length in parentheses) branch names 1C methyl n = 0 = () n = 9 = (11C) 2C ethyl n = 1 = propane (3C) n = 10 = dodecane (12C) CH4 = (1C) 3C propyl n = 2 = (4C) n = 11 = tridecane (13C) 4C butyl n = 3 = pentane (5C) n = 12 = tetradecane (14C) 5C pentyl n = 4 = hexane (6C) n = 13 = pentadecane (15C) H3C (CH2)n CH3 6C hexyl n = 5 = heptane (7C) n = 14 = hexadecane (16C) 7C heptyl chain length = n + 2 n = 6 = octane (8C) n = 15 = heptadecane (17C) 8C octyl n = 7 = (9C) n = 16 = octadecane (18C) 9C nonyl n = 8 = decane (10C) n = 17 = nonadecane (19C) 10C decyl cycloalkanes n = 3 = n = 9 = cycononane n = 4 = n = 10 = (CH ) n = 5 = n = 11 = 2 n n = 6 = n = 12 = n = 7 = n = 13 = n = 8 = n = 14 = ring size = n a. 2' 1' 3' structure to name hint 10 12 2' 9 11 1' 1' 8 2' 7 5 2' 6 4 1' 3' 3 1' 2 1" 2' 1" 1 = a branch point

Y:\files\classes\Organic Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc b. structure to name hint 6 5 8 7 9 7 4 2 1 3' 1' 3 3' 2' 2' 3' 3' 1" 1' 1" 1" 2" c. structure to name hint 1" 6 10 8 4 2 9 7 5 3 1 1" 1' 2' 3' 5' 2" 4' 1' 1' 6' 2' 2' 7' 1" 5' 3' 6' 3' 4' 5' 4' 2" 3"

1" 1" answers a. 2,2-dimethyl-3,10-diethyl-4-propyl-7-(1-methylethyl)-8-(1-methylpropyl)dodecane b. t rans-1-(1-methyl-2-ethylpentyl)-4-(2-methylpropyl) c. 1-(2-methyl-3-ethylcyclopentyl)-4-(3-propylcycloheptyl)-8-(4,4-dimethylcyclohexyl)decane

Alkenes prefix = none suffix = -ene

alkenes (always a suffix on the stem name) Condensed line formula CH3CHCHCO2H O 3D H 4 R R CH2C(CH3)2 O H O

CC 2D H C C 3 1 OH 3 1 OH 2 R R C C 4 2 2 O but-2Z-enoic 1 3 H suffix: #-ene H but-2E-enoic acid IUPAC: methylprop-2-ene H E = high priority opposite side prefix: none Z = high priority same side common: Alkenes a. 2

structure to name hint 1 3 2E stereochemistry 1 1 3 5 2 2 4 2 b. structure to name hint 1' 6 1 7 5 1 4 3Z stereochemistry 2 4 2 1 3 3 2' 2 1'

Y:\files\classes\ Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc c. 2' structure to name hint 3' 2 1' 1 3 3E stereochemistry 4 1 1 3 5 2 2 6 2

1' 1" 2' 5' 3' 4'

1" 2" d. structure to name hint 1" 3' 1 2 3 2' 2 1' 1E stereochemistry 1 2 1 2 4 1' 1 2 8 1' 2

6 2' 1 7 5 2' 3' 1 1Z stereochemistry e. 5' 3' 1 1 structure to name hint 1 6' 4' 5' 2' 1 7' 2E stereochemistry 4Z stereochemistry 2' 1" 2" 8' 3' 1' 4' 1 2 3' 1 3 1' 2 1' 1 3 5 2' 2 1 2' 2 4 6 2 2 1 7 8 9 5E stereochemistry 2Z stereochemistry answers a. pent-2E-ene b. 4-ethyl-6-methylhept-3Z-ene c. 3-propyl-4-(2-methyl-4-ethylcyclopent-3-enyl)hex-3E-ene d. 3-(1-methylprop-2-enyl)-4-(prop-1Z-enyl)cyclooct-1E-ene e. 3-(1-ethylpropyl)-6-(cycloocta-2E,4Z-dienyl)nona-2Z,5E-

Alkynes prefix = none suffix = -yne

alkynes (always a suffix on the stem name) CH3CCCO2H HCCCH CO H 3D 2 2 H O O 2D O H C H 1 C 2 4 C C C C OH 3 1 OH R 3 2 IUPAC: ethyne H 4 suffix: #-yne H O but-2-ynoic acid but-3-ynoic acid prefix: none common: E/Z is not possible with alkynes

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc Alkynes a. hint structure to name 2' 3' 3 1" 2 4 4' 1 1' 1" 5 b. 1' structure to name hint 5 4 6 8 1 3 7 9 2

1' 1' c. structure to name hint 1" 1 3' 9 8 1' 2' 2 4' 7 3 1" 6 4 5 2" d. structure to name hint 5 3 1 6 4 2 7

1" 1' 6' 2' 5' 3' 4' e. structure to name hint 7 5 3 8 6 4 2 9 1 10 11 1" 1' 6' 2' 5' 3' 4'

answers: a. 4-(4-methylcyclobut-2-enyl)-4-methylpent-1-yne b. 2,2,7-trimethylnon-3-yne c. 7-(-1-methyl-2-ethylbut-2E-enyl)cyclonon-1Z-en-4-yne d. 4-(6-methylcyclohex-3-enyl)hept-1-en-6-yne e. 6-(6-methylcyclohexa-1,3-dienyl)undec-3E-en-1,8,10-triyne

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc Combinations of alkenes and alkynes prefix = none suffix = -#-en-#-yne

alkenes and alkynes (always a suffix on the stem name, -#-en-#-yne) 3D O R Condensed line formula H O H C CCR H2CC(CH3)CCCH3 1 OH H C C C C 2 R C 2D 5 3 C C 6 R O 4 H suffix: #-en-#-yne H H hex-4Z-en-2-ynoic acid prefix: none IUPAC: 2-methylpent-1-en-3-yne

Aromatics have many special names, for now we will only use phenyl and benzyl prefixes

aromatics (2D) 3D aromatic IUPAC: methylbenzene branches H R R H common: H H benzyl C C H C C H C C R C C R C C CH H C C C H H CC H CC H phenyl C C R R H H many special names H H (2D) 3D aromatic H H H H H C C H C C H C C C C C C C C C H H CH H C C C C CC H C C H H H H H H H H 1-phenylpent-3E-en-1-yne

Carboxylic prefix = carboxy (we won’t use this one) suffix = -oic acid

Generic Functional Group Pattern Specific Example Specific Example in ordero of nomenclature priority Using Suffix (2D and 3D) Using Prefix when in our course. when highest priority FG lower priority FG 1. (2D) carboxylic acid (3D)

O Condensed line formula IUPAC: ethanoic acid O H H prefix example C H common: RCO2H or HO2CR C C R O #-carboxy H O RCH(CO H)R' H suffix: -oic acid 2 O not used in our course FG on FG on C H (acids are the highest priority prefix: #-carboxy the right the left H3C O group that we use) FG in the carbonyl (2D) middle (C=O) is possible

Carboxylic acids a. structure to name O O O O hint Functional groups 1. carboxylic acid 6 4 2 2. OH 7 5 3 1 OH 3. Cl Cl 8 4. O OH 9 O OH 5. 6. 7. acid chloride O O 1'

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc b. structure to name hint Br O 8 Br O Functional groups 1. carboxylic acid 2. 6 4 2 C OH 7 5 3 1 3. bromo C OH 4. alkene N N 5. NH 2 NH2 6. O NH2 O NH 2 c. O structure to name hint O

O H O H 9 Functional groups H NO2 O H 8 NO2 O 1. carboxylic acid 2. ester 6 4 2 3. nitro 7 5 3 1 4. OH OH 5. ketone 6. alkene O O 7. aldehyde O O O O

d. structure to name hint O O 6

5 OH 1 OH 2 4 3 answers: a. 2-hydroxy-5-oxo-6-methoxy-9-chlorocarbonylnon-3E-en-8-ynoic acid b. 2-amido-3-bromo-6-amino-7-cyanooct-3Z-enoic acid c. 2-methoxycarbonyl-3-nitro-5-formyl-6,9-dioxo-7-(prop-1E-enyl)nonanoic acid d. 2-methylbenzoic acid

Anhydrides prefix = too complicated for us suffix = -oic -oic anhydride

2. anhydride (2D) Condensed line formula anhydride (3D) IUPAC: ethanoic propanoic anhydride O O RCO2COR' or ROCO2CR' H H O O H C C C CH3 R O R C H C O C 3 H H 2 prefix example H O C H suffix: -oic -oic anhydride (2D) (just one -oic anhydride, O O O C C O if symmetrical) 3 1 H 4 H 2 prefix: #-acyloxyalkanecarbonyl O O OH (prefix not required for us) carbonyl resonance 4-acyloxyethanecarbonylbutanoic acid (C=O) is possible (prefix not required for us - too difficult)

Anhydrides a. structure to name O O hint O O

2 2 O 3 11O 3

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc b. structure to name hint Functional groups 1. anhydride O O O O 2. phenyl 3. alkene 4 2 2 4 331 O 1 5 O c.

structure to name hint O O O Functional groups O O O 1. anhydride 6 2 4 6 2. ether 3. alkene 5 O 1 3 5 O 1 4. aromatic 2 4

3 answers: a. propanoic anhydride (since it is symmetrical you only have to write the name one time) b. 3-methylbutanoic 3-phenylpent-3Z-enoic anhydride c. benzoic 3-methoxyhex-3Z-enoic anhydride

Esters prefix = #-alkoxycarbonyl prefix: “ branch” on suffix = -oate

3. ester (2D) alkyl name (goes in front as separate word) ester (3D) H H H IUPAC: propyl ethanoate O C Condensed line formula C O C common: propyl C R' H H R O RCO2R' or R'O2CR H H C C H O H H2 RCH(CO2CH3)R' H C C CH3 O H C O C prefix example prefix: alkyl suffix: -oate (in longest chain) 3 H2 O O (2D) prefix: #-alkoxycarbonyl (as a branch) 3 1 carbonyl resonance 4 2 (C=O) is possible O OH 4-methoxycarbonylbutanoic acid

a. structure to name O O 1" 1" hint N 2' 4' 6' N 1" O 1 O 1' 3' 5' 2 Functional groups 3 1. ester 2. alkyne 3. aromatic 4. alkene 5. amine b. structure to name hint 1' Functional groups SH O S SH O S 1. ester 2. alkene OH 2 3' OH 3. nitrile 6 4 4. ether O 5 3 1 O 1' 2' 4' 5. 6. alkene O C O C 7. 8. alcohol 1' N N

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc c. structure to name hint O O O O O O Functional groups 1. ester 2' 4 2 2. H O H 5 3 1 O 1' 3' 3. amide 4' 4. ketone SH SH 1' 5' 5. thiol 6' 6. aldehyde 2' NH 7. alkene 2 OH 3' NH2 OH 8. alkyne 9. alcohol

O O d. structure to name O 6 O Functional groups O 5 1 1. ester 2. aromatic O 3. bromo 2 4 4. nitro O2N 3

Br answers: a. 2-benzyl-3-methyl-6-(N,N-dimethylamino)hex-2E-enyl 3-phenylprop-2-ynoate b. 3-methylthio-4-hydroxybut-2Z-enyl 2-cyano-4-methoxy-5-mercaptohex-2E-enoate c. 6-hydroxyhex-2E-en-4-ynyl 2-(2-amidecyclopropyl)-3,5-dioxo-4-mercaptopentanoate d. phenyl benzoate benzyl 3-bromo-4-nitrobenzoate

Acid Chlorides prefix = #-chlorocarbonyl suffix = -oyl chloride

4. acid chloride (2D) carboxylic acid (3D) prefix example IUPAC: ethanoyl chloride O Condensed line formula O O Cl common: acetylchloride C RCOCl or ClOCR H 3 1 R Cl 4 2 C C O Cl OH RCH(COCl)R' H suffix: -oyl chloride H O C 4-chlorocarbonylbutanoic acid H C Cl prefix: #-chlorocarbonyl 3 (2D) carbonyl resonance (C=O) is possible, but weak because of the poor overlap of the 3p orbital with the 2p orbital

Acid chlorides a. structure to name hint 2' Functional groups 1. acid chloride O H O H 1' OH NH O O 2. fluoro 2 OH NH2 O O 3. alkene 4. ether 8 6 4 2 5. sulfide / thioether Cl 9 7 5 3 1 Cl 6. aldehyde 7. 8. amine O N S F O N S F 9. ketone O O 10. alcohol

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc b. 2' structure to name hint 1' Functional groups N O O N O O 1. acid chloride 2. nitro C O C 8 O 3. ester 7 4. thiol 6 4 2 5. amide Cl 5 3 1 Cl 6. alkyne 7. nitrile

SH NO2 SH NO2 O NH O NH 2 2 c. structure to name O O

Cl Br

answers: a. 2-fluoro-3-(propoxy)-4-methylthio-5-formyl-6-nitroso-7-amino-8-oxo-9-hydroxynon-2E-enoyl chloride b. 2-nitro-3-ethyoxycarbonyl-4--6-carbamoyl-8 –cyanooct-7-ynoyl chloride (sulfanyl = mercapto) (carbamoyl = amido)) c. benzyol chloride benzyol d.

Amides prefix = #-amido or #-carbamoyl suffix = -amide use “N” prefix instead of a number

o o o o 5. (1 ,2 ,3 ) (2D) 3 amide (3D) IUPAC: N-ethyl-N-methylethanamide H H O Condensed line formula H H common: N-ethyl-N-methylacetamide alkyl C C O C R' H H RCONR2 or R2NOCR H2 R N H N C C C ' H H3C N CH3 prefix example R" RCH(CONH2)R alkyl C C H O O H CH when highest priority functional group H (2D) 3 1o amides: suffix: -amide O H N 3 1 OH 2o amides: prefix: N-alkyl suffix: -amide 2 4 2 3o amides: prefix: N-alkyl-N-alkyl suffix: -amide carbonyl resonance (C=O) 4-amidobutanoic acid is possible, it is especially or prefix when lower priority functional group: strong in amides prefix example o 4-carbamoylbutanoic acid 1 amides: prefix: #-amido or #-carbamoyl O O 2o amides: prefix: #-(N-alkylamido) or #-(N-alkylcarbamoyl) H2 3o amides: prefix: #-(N-allkyl-N-alkylamido) or #-(N-alkyl-N-alkylcarbamoyl) C H C N 3 1 OH 3 4 2

CH3 4-(N-ethyl-N-methylamido)butanoic acid Amides a. structure to name N3 O hint N3 O N O N O 6 Functional groups 1. amide 4 2 2. amine O2N NH2 O N 5 3 1 NH 3. nitroso 2 2 4. nitro 5. NH NH 2 2

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc b. hint structure to name O O 2 1 Functional groups N 7 3 N H H 1. amide 6 4 2. nitrile C 5 C 3. alkyl branch 4. alkyne O N O N 5. ketone c. O structure to name hint

N benzyl phenyl

answers: a. 2-amino-3-nitroso-5-nitro-6-azidohexanamide b. N-ethyl-2-cyano-3-(1-methylethyl)-6-oxohept-4-ynamide c. N-benzyl-N-phenylbenzamide d.

Nitriles prefix = #-cyano suffix = -nitrile (retain the final “e”)

6. nitrile (2D) nitrile (3D) IUPAC: ethanenitrile prefix example N Condensed line formula H N C common: R RCN or NCR C C N C O H suffix: nitrile N 3 1 RCH(CN)R' H (don't drop the final C 4 2 OH "e" of the stem name) nitrile resonance H C 3 (2D) (CºN) is possible 3-cyanobutanoic acid prefix: #-cyano a. structure to name hint OH OH N Functional groups N 1. nitrile ON 2 C ON C 3 1 2. ether 4 3. alcohol 4. nitoso 5 O 5. alkene O 2' 6 1' b. structure to name O H hint O H 2' Functional groups 1. nitrile 1' 3 2. alkene branch H 2 3. aldehyde H 8 6 4 C 7 5 4. alkyne C 1 5. ketone 6. aldehyde in chain O O N O O N

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc c. O structure to name O hint

N 3' 2' Functional groups 2 N C N 4' 1' 1. nitrile 3 C C 5' 2. cycloalkane 1 3. ketone 4. alcohol OH 4 6 OH 5 answers: a. 2-ethoxy-3-hydroxy-4-nitrosohex-4Z-enenitrile (don’t drop the final “e” because nitrile starts with a consonant) b. 2-ethenyl-3-formyl-6,8-dioxooct-4-ynenitrile c. 3-(2-oxo-5-hydroxycyclopentyl)benzonitrile

Aldehydes prefix = #-oxo (if at the end of the longest chain) suffix = -al #-formyl (if a side branch on the longest chain)

7. aldehyde (2D) aldehyde (3D) IUPAC: ethanal Condensed line formula H O common: prefix examples RCHO or OHCR C O C O H H O O O R H RCH(CHO)R' C 5 3 1 suffix: -al H C 4 2 H H3C H H OH prefix: #-oxo (if part of longest chain) carbonyl resonance (2D) (C=O) possible 3-formyl-5-oxopentanoic acid #-formyl (if branch off of longest chain) Anhydrides a. 3' structure to name hint 2'

O 1' O Functional groups 1. aldehyde 2. etheer 8 6 4 2 5 1 3. ketone H 7 3 H 4. alkene 5. alcohol OH O O OH O O b. structure to name SH O hint 1" SH O Functional groups 5' 6' S 1. aldehyde 4' 7' 2 3 1 2. etheer H 3' H 3. thiol 2' 1' H H 6 4 4. alkyne O 5 O 5. ketone 6. cycloalkadiene 7. aldehyde side group O O O O 8. sulfide / thioether c. O O O hint structure to name 6 N N 3 Functional groups 3 H H 5 1 1. aldehyde H 2. aromatic alcohol () 2 3. azide 4 OH OH 3 answers: a. 2-methoxy-4-oxo-5-(prop-1E-enyl)-6-hydroxyoct-2Z-enal b. 2-methoxy-3-mercapto—6-oxo-6-(3-formyl-7-methylthiocyclohepta-2E,5Z-dienyl)hex-4-ynal

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc c. 2-hydroxy-5-azidobenzaldehyde

Ketones prefix = #-oxo suffix = -#-one (sounds like cone)

8. ketone (2D) ketone (3D) Condensed line formula H H O IUPAC: pentan-2-one C prefix example H R1COR2 or R2OCR1 C H H former: 2-pentanone O O R R' H H C O RCH(COCH )R' 3 C 3 1 C O 4 2 suffix: -#-one C C OH H H2 H H prefix: #-oxo (older = #-keto) H H C C H3C C CH3 3-oxobutanoic acid carbonyl resonance H2 (C=O) possible (2D)

Ketones a. structure to name Cl O hint Cl O 7 5 3 1 Functional groups 8 6 4 2 1. ketone 9 2. diene 3. benzyl 10 4. chloro 5. phenyl 6. alkyne

b. structure to name O OH hint O OH Functional groupsketone 4 2 1 1. alcohol 5 3 2. ketone 6 8 3. cycloalkadiene 9 7 4. amine 1' 5 alkene H2N H2N 2' 8' 7' 6. alkyne S S 4' 6' 7. sulfide / thioether 3' 5' c. O structure to name O

answers: a. 2-benzyl-6-chloro-7-phenyldeca-3E,5Z-dien-9-yn-2-one b. 1-hydroxy-4-(2-aminocycloocta-5Z,7E-dienyl)-8-methylthionon-4E-en-6-yn-3-one c. acetophenone (1-phenylethan-1-one) benzophenone d.

Alcohols prefix = #-hydroxy suffix = -#-ol

9. alcohol (2D) Condensed line formula alcohol (3D) IUPAC: propan-1-ol prefix example H H former: 1-propanol OH O O RCH2OH or HOH2CR H H R H C H common: n-propyl alcohol 3 1 RCHOHR' C 4 2 suffix: -#-ol C O OH H H2 H C OH prefix: #-hydroxy H 3-hydroxybutanoic acid H3C C H (2D) 2

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc a. structure to name hint 2 4 6 8 1 3 5 7 Functional groups 1. alcohol 2. 2o amine OH NH O OH NH O 3. alkene 2' 4' 4. ether 1' 1' 3' 1" b.

structure to name hint 3" OH OH 3' Functional groups 2' 4' 2" 1. alcohol 1' 5' 2. nitroso 1 6' 2 1" 3. alkyne O O 4. alkene 3 5. NO Br 4 NO Br 6. bromo 5 7. ether 6 c. structure to name OH OH

answers: a. 4-(N-methylamino)-6-(1-methylbutoxy)oct-5Z-en-2-ol b. 1-nitroso-1-(5-propoxy-6-bromocyclohex-2-enyl)-5-methylhex-5-en-3-yn-2-ol c. phenol d.

Thiols prefix = #-mercapto or #-sulfanyl suffix = -#-thiol

10. thiol (2D) thiol (3D) Condensed line formula IUPAC: propan-1-thiol prefix example S H H SH O R H H H common: propyl mercaptan R CH SH or HSH CR 1 2 2 1 C H 3 1 suffix: -#-thiol C 4 2 (don't drop the final C S H2 OH R1CHSHR2 H C SH "e" of the stem name) H H H C C 3-mercaptobutanoic acid 3 (2D) prefix: #-mercapto H2 3-sulfanylbutanoic acid #-sulfanyl a. structure to name hint HS 5 7 9 HS 8 Functional groups 4 6 3 1. alkyne 2. thiol 2 O O 1' 3' 3. alkene 2' 4' 4. ether 1 1" b. structure to name 1' hint Functional groups 1. thiol 6 SH 5 7 NO 2. alkyne SH NO2 1' 2 3. alkene 4 1' 4. alkyl branch 2 3 5. cycloalkene branch 2' 6. azide N N3 1 4' 3 7. nitro 3'

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc c. structure to name hint 4 2 5 SH 3 1 SH Functional groups 1. thiol 2. benzyl 3. phenyl

answers: a. 7-(3-methylbutoxy)non-6Z-en-1-ynethiol (retain the “e” because thiol starts with a consonant) b. 2,5-dimethyl-6-(2-azidocyclobut-2-enyl)-7-nitrohept-3-ynethiol c. 4-benzyl-5-phenylpentanethiol d.

Amines prefix = #-amino suffix = -#-amine (if additional alkyl groups are on the nitrogen, use an “N” prefix)

11. (1o, 2o, 3o) (2D) Condensed line formula 3o amine (3D) R' RNH H NR H H H 2 2 H H H IUPAC: N-ethyl-N-methylpropan-1-amine N R(NR')R" C C H R R" C former: ethylmethylpropylamine RCH(NH2)R' C N C H when highest priority functional group H o H H H 1 amines: suffix: -amine H prefix example 2o amines: prefix: N-alkyl suffix: -amine C o H H 3 amines: prefix: N-alkyl-N-alkyl suffix: -amine NH O CH3 3 1 prefix when lower priority functional group: H2 4 2 1o amines: prefix: #-amino C N CH3 OH H C C C 2o amines: prefix: #-(N-alkylamino) 3 H2 H2 (2D) o 3-(N-methylamino)butanoic acid 3 amines: prefix: #-(N-allkyl-N-alkylamino) Amines a. 1' NH2 structure to name NH2 hint

3 1 4 2 Functional groups 1' 1. amine 5 2. alkyl branches 6 3. alkene 7 1' 4. alkyne 8 1" 2' b. structure to name 3' 4' hint Functional groups 2' 5' 1' 1. amine Br Br 2. alkyl branch 3. alkene H H 4. ether N NO2 N 1 3 5 NO2 5. cycloalkene branch 2' 2 4 1' 6. bromo 7. nitro O 1" O 1'

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc c. structure to name hint 3' 4' 2' 2' 5' 1" Functional groups S 1' S 2" 1. amine 1' 2. alkyl branches 3. alkene N N 3 N 1 3 N3 4. ether 2' 1' 2 4 5. cycloalkene branch 3' 5 6. sulfide / thioether 7. azide O 1" O 1' 6 answers: a. 3-(1-methylethyl)-4,7-dimethyloct-3E-en-5-yn-2-amime b. N-(1-methylethyl)-3-methoxy-4-(5-bromocyclopent-2-enyl)-5-nitropent-2Z- c. N-ethyl-N-(1-methylethyl)-3-methoxy-4-(5-ethylthiocyclopent-2-enyl)-5-azidohex-2Z-enamine d.

Ethers prefix = #-alkoxy suffix = none

12. ether (2D) Condensed line formula ether (3D) O ROR' H H H R1 R2 H H H C C H C prefix example suffix: none RCH(OCH3)R' C O C H IUPAC: 1-ethoxypropane prefix: #-alkoxy (< 5C) H H H H O O common: ethyl propyl ether #-alkyloxy ( 5C) H 3 1 2 4 2 C O CH3 OH H3C C C H2 H2 (2D) 3-methoxybutanoic acid a. structure to name hint 4 Functional groups 2' 4' 1. ether 3 1 O 1' 3' O 2 2. phenyl 3. alkyl branches

b. structure to name hint O O 1' 3' 2 2' 4' 3 1 4 6 Functional groups 5 1. ether 2. phenyl 3. benzyl

c. O structures to name O

O answers: a. 1-(2-methylbutoxy)-3-phenylbutane or (2-methylbutyl 3-phenylbutyl ether) b. 1-(1-phenylbutoxy)-4-benzylcyclohex-3-ene c. ethoxyethane / / ethyl ether / ether / THF d.

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc Thioethers prefix = #-alkylthio suffix = none

12. sulfide (2D) Condensed line formula thioether or sulfide (3D) S RSR' H H H R1 R2 H H H C C H RCH(SCH )R' C prefix example suffix: none 3 C S C IUPAC: 1-ethylthiopropane H H S O prefix: #-alkylthio H H H former: ethyl propyl sulfide 3 1 H 4 2 2 OH C S CH3 H3C C C (2D) H H 3-methylthiobutanoic acid 2 2 Thioethers a. , b. , c.

S S

S

answers: a. 1-propylthiocyclohexa-1,3-diene b. benzyl phenyl sulfide c. 2-ethylthiopent-4-ene d.

Halogens prefix = #-fluoro, chloro, bromo or iodo suffix = none

12. (2D) bromoalkane (3D) prefix example X = -F = fluoro Condensed line formula Br X H H X = Cl = chloro H H (2D) F O X = Br = bromo CH CH RCH2 Cl or ClH2CR C X = I = iodo C H3C CH3 R R' C H 3 1 OH H 4 2 suffix: none RCHClR' H IUPAC: 2-bromopropane Br prefix: #-halo common: isopropyl bromide 3-fluorobutanoic acid

Halogens a. Br Br

I I 2' 4' 6 1' 3' 5' 5 1 4 3 2 Cl F Cl F answers: a. 1-(2-methyl-5-bromopentyl)-2-fluoro-4-chloro-5-iodocyclohexa-1,3-diene

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc Nitroso prefix = #-nitroso suffix = none

12. nitroso (2D) Condensed line formula nitroso (3D) prefix example H 2 IUPAC: 1-nitrosopropane H C C RCH2 NO or ONH2CR H H O 3 N O C NO N O H C H2 2 RCH(NO)R' H C H C C O 3 1 C 3 4 2 suffix: none C N OH H H H2 H H prefix: #-nitroso (2D) 3-nitrosobutanoic acid

Nitro prefix = #-nitro suffix = none

nitroso (3D) 12. nitro (2D) Condensed line formula IUPAC: 1-nitropropane O H2 RCH2 NO2 or O2NCH2R H3C C C NO H H 2 N O H2 prefix example H2 RCH(NO2)R' C H3C C O H C C N suffix: none C H 2 O O H H prefix: #-nitro H H O N O (2D) resonance 3 1 4 2 OH resonance O 3-nitrobutanoic acid H2 H H H3C C O N O C N C H2 H C C O H H H H prefix = #-azido suffix = none

azide (3D) 12. azides (2D) IUPAC: 1-azidopropane Condensed line formula H2 H C C common: propyl azide 3 H C N RCH2 N3 or N3CH2R H H 3 2 N N N H2 N prefix example C RCHN R' H C H3C C N 3 C C N suffix: none H N3 O H H 2 H H prefix: #-azido 3 1 (2D) 4 2 OH resonance resonance 3-azidobutanoic acid

H N H H 2 H3C C N N N N C C N H C H2 C H H H H a. N 3 structure to name N3 hint NO NO 4' 8 Functional groups 2' 1. alkyne 5' 3' 1' 7' 1 2 3 6 7 2. alkene 6' 8' 3. nitroso 5 4 4. nitro 5. cycloalkene NO 2 NO2 answers: a. 1-(4-azidocyclooct-2E-enyl)-3-nitroso-5-nitroocta-3Z,7-dien-2-yne

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc prefix = #-diazo suffix = none (not used in our course)

12. diazo (2D) diazo (3D) Condensed line formula H IUPAC: 1-diazobutane H3C C RCH N2 or N2CHR C N H H H H 2 2 C N N H2 N RC(N )R' C 2 H C H3C C N prefix example suffix: none C C C H N O H H 2 2 H H (2D) prefix: #-diazo H 3 1 2 4 OH resonance resonance 3-diazobutanoic acid

H N H 2 H H H3C C N C N N C C C H C H2 C H H H H H

Nomenclature Strategy Points to Consider 1. What is the highest priority group present? 2. What is the longest chain with that group? 3. Number that chain (ring) so that the high priority group gets the lowest number. 4. Identify branches and other functionality with those numbers. (Usually named as prefixes.) 5. Combine everything into one name with proper use of hyphens (between numbers and letters) and commas (between numbers and numbers). 6. Identify as E/Z for alkenes and R/S for chiral centers. Combine with the number which refers to each center, with the number written first. (3E, 5Z, 4S, 9R, etc.)

Here are a few names that can be written out as structures, opposite to the way we do it. a. 2,4-dimethylhexane b. 1,3,5,5-tetramethyl-1-cycloheptene c. trans-5-hepten-1-yne or 5E-hepten-1-yne d. 5-(4-methyl-2-cyclobutenyl)-1- e. trans-3-ethyl-1-isoproplycyclopentane f. cis-1-t-butyl-4-isobutylcyclohexane g. trans-2-cis-4-decadien-6,8-diyne or 2E,4Z-decadien-6,8-diyne h. 1-allyl-3-propargyl-6-vinylcyclodecane or 1-(2-propenyl)-3-(2-propynyl)-6-ethenylcyclodecane i. 1-hepten-6-yne j. 3-allyl-1-sec-butyl-1-cyclopropene or 3-(2-propenyl)-1-(1-methylpropyl)-1-cyclopropene k. 3-propyl-1-trans-6-octadiene or 3-propyl-1E,6-octadiene l. 7-(1,1-dimethylethyl)-4-(1-methylpropyl)-1-cycloundecyne m. 2,9 ,10-trimethyl-6-butyldodecane n. 1-(1,3-dimethylbutyl)-4-methyl-1,3,5,7-cyclooctatetraene o. 2,9,10-trimethyl-6-butyldodecane p. trans-(3,3-dimethylbutyl)-3-methylcyclooctane q. 7-(1,1-dimethylethyl)-4-(1-methylpropyl)-1-cycloundecyne r. 1-hepten-6-yne s. 1-trans-3-cis-7-cis-cycloundecatriene or 1E,3Z,7Z-cycloundecatriene t. 3-benzyl-6-ethyl-7-phenyl-2Z-

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc More Complicated Functional Group Combinations

O NH2 O H OH O O O O O

N O C NH2 SH Br Cl O O O H

Possible answer (each side is a separate word because this is an anhydride = 2 x “-oic” + anhydride)

1

1 3 2 5Z 3Z 2S 1 3 2 4 1 1 1 O NH2 O H OH O O O O O 12 4 2 2 6 8 10 N 5 3 11O 3 5 7 9 11 13 C 8 6 4 9 7 NH 1 SH Br 10 2 5 Cl O 1 2 9 2 3 O 2 O H 8 12S 11 4 33 1 4 7 1 4 3 2 5 6 3 2 5 4 10R 7 6

1 4 (space) 2S-amino-3-amido-4-phenyl-5-hydroxy-8,11-dioxo-9-methoxycarbonyl-10-cyanoundec-3Z-en-6-ynoic

2-(5-methylcyclopent-2-enyl)-3-benzyl-6-chlorocarbonyl-8-(4-heptylcyclonona-2E,4Z-dienyl)-9-formyl-

10R-mercapto-11-(1-methylpropoxy)-12S-bromotridec-5Z-enoic anhydride

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc More Complicated Functional Group Combinations

N O H O NH2 O O C O O Cl

O S H3C NH2 Cl SH O O OH O H

Possible answer (each side is a separate word, the first word is the name of the “alkyl” branch attached to the ester oxygen on the left side and the second part is the name of the branch with the on the right side). 1 1

3 2 4 1 5 2R 3Z 5E 2 3 1 4 N 1 1 O H O NH2 O O C O O Cl 1 4 6 2 2 4 6 8 10 12 5 3 O 3 7 9 11 7 1 5 13 2 3 S 10 8 H3C 9 NH2 Cl SH 1 12S 5 1 2 O O 2 OH 9 4 3 1 4 O 11 H 8 3 1 3 2 1 4 7 5 10S 3 2 6 2 3 5 4 4 5 4 1 7 6 8 6

(space) 2R-amino-3-formyl-4-benzyl-5,11-dioxo-8-hydroxy-9-chlorocarbonyl-10-methylthioundec-3Z-en-6-ynyl

2-(4-ethyl-5,5-dimethylcyclopent-2-enyl)3-phenyl-5-cyano-6-methoxycarbonyl-8-(4-hexyl-7-octylcyclonona-2E,5Z-dienyl)-

9-amido-10S-chloro-11-(1-ethylbutoxy)-12S-mercaptotridec-5E-enoate

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc Match each functional group with its name. 2D and condensed line formulas.

12O O O 3 O 4 O 5 O a. aromatic b. fluoro C H C C C H C C R' c. carboxylic acid R O R O R' R Cl R O R N d. 1o amine RCO COR H e. 2o amide RCO2H 2 RCOCl RCO2R' RCONH2 f. nitrile g. thiol 6 O 7 O 8 9 10 h. ether O O N i. bromo C R' C R' C j. acid chloride C C R N R N R R H R R' k. ketone H R" l. sulfide m. RCONHR' RCONR'R" (R  R'  R") RCN RCHO RCOR' n. nitro RCONR'2 (R'  R") o. 3o amide H p. alkene 11 12 13 H 14 15 R" O S q. aldehyde R H R H N N N r. nitroso R R' R H R R' s. alcohol t. iodo ROH RSH RNH2 RNHR' RNR'R" u. 2o amine v. alkyne w. chloro 16 17 19 20 18 Br Cl F o O S x. 3 amine R R R R R' R R' y. azido z. anhydride ROR' RSR' RBr RCl RF aa. 1o amide bb. diazo cc. ester 23 24 R 25 dd. alkene/alkyne 21 I 22 R R' O R C C C R R C C C N R C R C R O RI RCCR' R R R2CCR2 R RNO2 RCCCRCR2

26 27 28 29 R 30 H N R O N R R N N N N R2C RH RNO RN3 R2CN2 RC6H5

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc O 1 O 2 O O 3 O 4 O 5 C C H C C C C R' H R N R O R O R' R Cl R O o carboxylic acid chloride ester 1 amide H *2 prefix: #-carboxy*1 prefix: #-acyloxyalkylcarbonyl prefix: #-alkoxycarbonyl prefix: #-amido prefix: #-chlorocarbonyl or #-carbamoyl suffix: -oic anhydride (R = R') suffix: -oate suffix: -oic acid suffix: -oyl chloride (R' name as branch at front) -oic -oic anhydride (R  R') suffix: -amide O O O 6 7 8 9 10 O N C R' C C R' C R N R N C R H R R R' o aldehyde 2 amide 3o amide ketone H R" nitrile prefix: #-oxo- (in chain) prefix: #-oxo prefix: #-(N-alkylamido) prefix: #-(N-alkyl-N-alkylamido) prefix: #-cyano or #-formyl (as branch) #-(N-alkylcarbamoyl) #-(N-alkyl-N-alkylcarbamoyl) suffix: -#-one suffix: -nitrile suffix: #-al suffix: -amide suffix: -amide name R' as N-alkyl in front name R',R" as N-alkyl-N-alkyl in front

11 12 13 H 14 H 15 R" O S R H R H N N N R H R R' R R' alcohol thiol o 1 amine o 3o amine prefix: #-mercapto 2 amine prefix: #-hydroxy or #-sulfanyl prefix: #-amino prefix: #-(N-alkylamino) prefix: #-(N-alkyl-N-alkylamino)- suffix: -#-ol suffix: -#-thiol suffix: -#-amine suffix: -#-amine suffix: -#-amine

16 17 18 19 20 O S Br Cl F R R' R R' R R ether R sulfide bromoalkane chloroalkane fluoroalkane prefix: #-alkoxy (5C) #-alkyloxy (> 5C) prefix: #-alkylthio prefix: #-bromo prefix: #-chloro prefix: #-fluoro

suffix: none suffix: none suffix: none suffix: none suffix: none R 24 R 25 21 I 22 23 R' O *3 R C C C R R N C C C iodoalkane R C R R O alkyne C alkene alkenyne nitroalkane prefix: #-iodo R R R prefix: none prefix: none prefix: none prefix: #-nitro suffix: none suffix: -#-ene suffix: -#-yne suffix: -#-en-#-yne suffix: none

26 27 *3 28 29 R 30 R O N N *3 H R N N R N R N C nitrosoalkane azidoalkane diazoalkane alkane prefix: #-nitroso R aromatic prefix: #-alkyl prefix: #-azido prefix: #-diazo many special suffix: none suffix: -ane suffix: none suffix: none names *1: not used because we don't use any higher priority group 3 2 1 *2: not used because it is too complicated for our level 1 *3: formal charge and resonance is always present. 1 C C C 2 C 4 4 C 2 C 2 3 2 1 1 Possible stereochemical features include chiral centers, S = sinister "R and S" and pi bond configurations, "E and Z". R = rectus 2 1 (clockwise) (counter clockwise) Z = zussamen E = entgegen Numbers (1,2,3,4) indicate priority of groups based on atomic numbers. (both "1"s on same side) ("1"s on opposite side)

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc 2D structures and condensed line formulas

12O O O 3 O 4 O 5 O

C H C C C C R' C H R O R O R' R Cl R O R N

H RCO2H RCO2COR RCOCl RCO R' 2 RCONH2 carboxylic acid anhydride acid chloride ester 1o amide

6 O 7 O 8 9 10 O O N C C R' R' C R N R N C C R R H R R' H R" RCONHR' RCONR'R" RCN RCHO RCOR' o 2o amide 3 amide nitrile aldehyde ketone

11 13 H 14 H 15 R" O 12 S R H R H N N N R H R R' R R'

ROH RSH RNH2 RNHR' RNR'R" alcohol thiol 1o amine 2o amine 3o amine

16 17 18 19 20 Br Cl F O S R R R R R' R R'

ROR' RSR' RBr RCl RF ether sulfide bromoalkane chloroalkane fluoroalkane

R R 21 22 23 R' 24 25 O I C R C C R R C N R C C C R R O C R R R RCCR' RI R2CCR2 RCCCRCR2 RNO2 iodoalkane alkene alkyne alkenyne nitroalkane

26 27 28 29 N R 30 N R O R N H N N N R R2C

RNO RN3 RH R2CN2 RC6H5 nitrosoalkane azidoalkane diazoalkane aromatic alkane

Y:\files\classes\Organic Chemistry Tool Chest\Nomenclature\0 Functional Groups, nomenclature, 2D, 3D, structures b.doc