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OrgChem- Chap12 1 Chapter 12 Functional Groups II and Nomenclature II Functional group = “a group of atoms where the reaction takes place”

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Presentation on theme: "OrgChem- Chap12 1 Chapter 12 Functional Groups II and Nomenclature II Functional group = “a group of atoms where the reaction takes place”"— Presentation transcript:

1 OrgChem- Chap12 1 Chapter 12 Functional Groups II and Nomenclature II Functional group = “a group of atoms where the reaction takes place”

2 OrgChem- Chap12 2 12.1 Aromatic Hydrocarbons: arenes Complete definition of aromatic compound: Ch 16 Aromatic = 향기로운, 향기높은 strong odor & unusually stable (because of the conjugated p orbitals) non-polar, high mp, wide occurrence in nature Benzene Not cyclohexatriene Toluene Not methylbenzene Naphthalene Very stable isolated very early days of organic chemistry before the systematic names are made Basic nomenclature 1. parent name: benzene, toluene, naphthalene etc.

3 OrgChem- Chap12 3 2. The ring is numbered in the same manner as the ring of cyclohexane ① No number is needed if only one group is attached to the ring ② For rings with multiple substituents, begin numbering at one substituent and proceed in the direction that gives the lowest numbers to the remaining 4-butyl-1-ethyl-2-isopropylbenzene 3. disubstituted: o-, m-, p- or numbering (1,2-, 1,3-, 1,4-) ortho-, o- meta-, m-para-, p-

4 OrgChem- Chap12 4 m-propyltoluene or 3-propyltoluene Example 4. as substituents: phenyl (Ph), benzyl (Bn), tolyl p-dimethybenzene or 1,4- dimethybenzene Common name = p-xyrene phenyl benzyl biphenyl

5 OrgChem- Chap12 5 Physical properties of benzene melting point boiling point ( o C) Benzene 5.5 80 Cyclohexane 6.5 80 Hexane -94 69 Symmetric shape gives higher melting temp. Interaction between the molecules determine the boiling point Reactivity of benzene lower than alkene R-CH=CH-R + Cl 2 R-CHCl-CHCl-R Benzene + Cl 2 No rxn + Cl 2 + AlCl 3 (Lewis acid) Chlorobenzene + HCl Cl 2 + AlCl 3 = Cl + - AlCl 4 More electrophilic

6 OrgChem- Chap12 6 Conjugated p orbitals  very stable  found in a wide variety of natural source Ex) 1) Benzene 1825 Michael Faraday Oil residue  condensed from gas To light the street lamps of London 2) Estrone: femaile sex hormone (  469) 3) benzo[a]pyrene  carcinogen  After smoking, burned food

7 OrgChem- Chap12 7 practice:  468, Problem 12.1 & 12.2 Focus On:  469, structure proof for dibromobenzene  Application of benzene  obtained from cracking 1) Solvent 2) Production of styrene  Polystyrene 3) o-Xyrene, p-xyrene, toluene, cumene (isopropyl benzene); solvent

8 OrgChem- Chap12 8

9 9 12.2 Phenols 1.  3 x 10 9 lbs/yr: large production 2. Application; disinfectant, bisphenol A (polymer) 3. Stronger acid (pK a  10) than alcohols (16) Problem 11.5 practice:  472-3, Problem 11.3 ~ 11.6 Having a hydroxy group bonded directly onto an aromatic ring

10 OrgChem- Chap12 10 Parent name: phenol or other common names phenolcatechol phloroglucinol m-chlorophenol p-methylphenol p-cresol

11 OrgChem- Chap12 11 12.3 Aldehydes & Ketones Nomenclature: the longest chain with the carbonyl group alkanal / alkanone:  474 & 475 acetaldehyde acetoneacetophenonebenzaldehyde carbonyl group ethanal or acetaldehyde  from acetic acid 4-bromohexanal 4-ethyl-4-pentanal (double bond must be part of a root chain) Carbon-oxygen double bond Aldehyde: one hydrogen atom bonded to the carbonyl group Ketone: both of the atoms bonded to the carbonyl group must be carbons

12 OrgChem- Chap12 12 Benzaldehyde  derived from benzoic acid 2-methylcyclopentanecarboxaldehyde acetone (common) or 2-propanone 4-methyl-4-hexen-2-one or 4-methylhex-4-en-2-one 5-methyl-2-cyclohexen-1-one (ketone have the priority, double bond have lower #) 1,3-cyclohexendione

13 OrgChem- Chap12 13 acidic  -carbon: pKa  20 Properties of aldehyde polarity: alcohol > aldehyde > ether (boiling point is in the same order) H-bonding No H-bonding aldehyde can be oxidized to carboxylic acid, while ketone cannot (see  381, why? Study in ch 19). See  45

14 OrgChem- Chap12 14  Application of aldehyde and ketones  476-7  pleasant odors  perfumes and flavoring 1) citral: lemon odor found in lemon and orange 2) cinnamaldehyde: strong cinnamon odor found in cinnamon 3) vanillin: vanilla odor, component of natural vanilla 4) camphor: from camphor tree  liniments and inhalants ( 감염, 통증, 가려 움증 완화 ) 5) Muscone : from musk ( 사향 )

15 OrgChem- Chap12 15

16 OrgChem- Chap12 16 12.4 Carboxylic Acids: RCO 2 H carbonyl (C=O) + hydroxy (OH) 5-phenylhexanoic acid 3-butynoic acid 2-chlorocyclopentanecarboxylic acid benzoic acid Root with the carboxyl group at one end with the suffix –oic acid is added Cyclic compounds with the carboxy group attached to the ring use the name of the ring with the suffix- carboxylic acid

17 OrgChem- Chap12 17 Properties more polar & hydrogen bonding: high mp & bp acidic proton: pKa  5 AcOH (  3 x 10 9 lbs/yr), aspirin, ibuprofen( 항염증제 ):  479 phenylacetic acid carboxyl group terephthalic acid malonic acid Natural carboxylic acid  Ant (Latin: fomica)  formic acid HCO 2 H  Vinegar (Latin: acetum  acetic acid CH 3 CO 2 H  Butter (Latin: butyrum)  butyric acid CH 3 (CH 2 ) 2 CO 2 H, from rancid butter

18 OrgChem- Chap12 18

19 OrgChem- Chap12 19 12.5 Carboxylic Acid Derivatives (I): RCO-Y parent name: alkan(o)ic acid

20 OrgChem- Chap12 20 acryloyl chloridesuccinic anhydrideethyl acetate N,N-dimethylformamideacetonitrilemonosodium glutamate (MSG) u practice:  483, Problem 12.14~15

21 OrgChem- Chap12 21 Acid chloride ----ic acid  ---yl chloride Acetic acid Acetyl chloride Ethanoic acid Ethanoic chloride + Acid anhydride Loss of water 2-butenoyl chloride Acetic anhydride Ethanoic anhydride ---ic anhydride Benzoic anhydride  benzoic acid

22 OrgChem- Chap12 22 Ester ----yl ---ate Alcohol Carboxylic acid (2-methylbutyl) 3-methyl-1-cyclohexanecarboxylate Propyl benzoate  propanol + benzoic acid 2-methylbutanol + 3-methyl-1-cyclohexanecarboxylic acid

23 OrgChem- Chap12 23 Amide Primary amide Secondary amide Tertiary amide ----e  ---amide Pentane  pentanamide N-ethyl-4-methyl-2,5-hexdienamide --ic acid, --oic aicd  ---amide N,N-dimethylformaide (DMF) N,N-dimethylacetamide (DMAc)

24 OrgChem- Chap12 24

25 OrgChem- Chap12 25 Nitrile or cyano group -H 2 O +NH 3 -H 2 O ----  ---nitrile ----oic acid ----ic acid  ---nitrile 1) 2) Complex compound  cyano 3-pentynenitrile Benzonitrile  benzoic acid Methyl 4-cyanobenzoate (priority) see p. 490 table 11.3

26 OrgChem- Chap12 26 Carboxylate salt carboxylate anion + cation Sodium acetateAmmonium 3-methylbenzoate characteristics: mp & bp Polarity , bp & mp   interaction  Order: HC < ether < ester < aldehyde < ketone < alcohol < carboxylic acid < amide H-bonding amides: charged resonance structure  very polar, highest mp and bp --ic acid  cation ---ate

27 OrgChem- Chap12 27

28 OrgChem- Chap12 28 Acid halide, acid anhydride, and nitrile  rare in nature  too reactive with water Ester and amide  abundant in nature  relatively stable  485-6 Ester; pleasant order of fruit and flower  isopentyl acetate (CH 3 CO 2 CH 2 CH 2 CH(CH 3 ) 2 : banana odor methyl butanoate (CH 3 CH 2 CH 2 CO 2 CH 3 ): rum (liquor), 당밀, 사탕수수를 발 효 시킨 액체 향 fat: ester  glycerol + octadecanoic acid (= stearic acid)  485 Amide; physiological activity  acetaminophen: pain reliever diethylamide of lysergic acid: hallucinigen ( 환각제 ) DMF and DMAc: aprotic polar sovent no acidic proton but very polar  even some salts can be dissoved

29 OrgChem- Chap12 29 Elaboration: fragrance & flavor,  486~7 –hydrolysis of ester & oxidation of aldehydes  Carboxylic acid Ester, aldehyde, ketone: pleasant odor  major component of natural scent and flavors isopentenyl acetate: juicy fruit gum ethyl phenylacetate: honey benzyl acetate +  -pentylciccamaldehyde: jasmine butanal: buttery Acid: undesirable odor  major component of natural scent and flavors butanoic acid: rancid butter hexanoic acid (=caproic acid): smell of goat 2-methylpropanoic acid: component of sweat

30 OrgChem- Chap12 30 12.6 Sulfur and phosphorus Compound Sulfur  directly beneath oxygen in the periodic table  similar to oxygen  d-orbital: six bonds are possible  RSH: thiols (mercaptans); alkanethiol CH 3 CH(CH 3 )CH 2 CH 2 -SH: 3-methyl-1-butanethiol stinky odor, stronger acid, better nucleophile  R-S-R’: sulfides; alkylalkyl sulfide (CH 3 -S-CH 3 : dimethyl sulfide)

31 OrgChem- Chap12 31

32 OrgChem- Chap12 32 sulfoxides & sulfones: DMSO & dimethyl sulfoxide sulfonic acids: strong organic acid, derivatives: similar to those of carboxylic acids

33 OrgChem- Chap12 33

34 OrgChem- Chap12 34 Phosphorus: P NH 3 : amine  nitrogen PH 3 :phosphine  phosphorus PH 3  phosphine  phosphate  phosphoric acid (H 3 PO 4 ) triphenyl phosphine: PPh 3 Dialkyl hydrogen phosphate PH 3 : phosphine, a toxic gas with bad odor PPh 3 : good nucleophile & transition metal ligand (RO) 2 P(O)OH: phosphate, backbone for RNA/DNA phosphatidylcholine: constituent of membranes practice:  491 Problem 12.17~18

35 OrgChem- Chap12 35

36 OrgChem- Chap12 36

37 OrgChem- Chap12 37

38 OrgChem- Chap12 38

39 OrgChem- Chap12 39

40 OrgChem- Chap12 40

41 OrgChem- Chap12 41 12.7 Nomenclature of Compounds with Several Functional Groups C  C-OH :–ynol C=C-C=C-CO- : dienone  priority  492 Table 12.3, next page  High priority, in the suffix 5-hydroxy-3-hexanone Ethyl 3-oxobutanoate 3-cyano-6-hydroxy-4-pentenal O

42 OrgChem- Chap12 42

43 OrgChem- Chap12 43 Common name: often more convenient for very complicated compounds,  494


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