1 / 43

Chapter 12 Functional Groups II and Nomenclature II

Chapter 12 Functional Groups II and Nomenclature II. Functional group = “a group of atoms where the reaction takes place”. 12.1 Aromatic Hydrocarbons: arenes Complete definition of aromatic compound: Ch 16 Aromatic = 향기로운 , 향기높은

Download Presentation

Chapter 12 Functional Groups II and Nomenclature II

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript


  1. Chapter 12 Functional Groups II and Nomenclature II Functional group = “a group of atoms where the reaction takes place” 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 Basic nomenclature 1. parent name: benzene, toluene, naphthalene etc. Very stable isolated very early days of organic chemistry before the systematic names are made Toluene Not methylbenzene Naphthalene Benzene Not cyclohexatriene OrgChem-Chap12

  3. 2. The ring is numbered in the same manner as the ring of cyclohexane • No number is needed if only one group is attached to the ring • 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- OrgChem-Chap12

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

  5. Physical properties of benzene melting point boiling point (oC) 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 + Cl2 R-CHCl-CHCl-R Benzene + Cl2 No rxn + Cl2 + AlCl3 (Lewis acid) Chlorobenzene + HCl Cl2 + AlCl3 = Cl+ -AlCl4 More electrophilic 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 OrgChem-Chap12

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

  8. OrgChem-Chap12

  9. 12.2 Phenols Having a hydroxy group bonded directly onto an aromatic ring  3 x 109 lbs/yr: large production Application; disinfectant, bisphenol A (polymer) Stronger acid (pKa 10) than alcohols (16) Problem 11.5 practice:  472-3, Problem 11.3 ~ 11.6 OrgChem-Chap12

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

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

  13. Properties of aldehyde polarity: alcohol > aldehyde > ether (boiling point is in the same order) H-bonding No H-bonding See  45 acidic a-carbon: pKa  20 aldehyde can be oxidized to carboxylic acid, while ketone cannot (see  381, why? Study in ch 19). 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,가려움증 완화) • 5) Muscone : from musk (사향) OrgChem-Chap12

  15. OrgChem-Chap12

  16. 12.4 Carboxylic Acids: RCO2H carbonyl (C=O) + hydroxy (OH) Root with the carboxyl group at one end with the suffix –oic acid is added 5-phenylhexanoicacid 3-butynoicacid 2-chlorocyclopentanecarboxylicacid Cyclic compounds with the carboxy group attached to the ring use the name of the ring with the suffix- carboxylic acid benzoic acid OrgChem-Chap12

  17. carboxyl group malonic acid terephthalic acid phenylacetic acid • Natural carboxylic acid • Ant (Latin: fomica)  formic acid HCO2H • Vinegar (Latin: acetum  acetic acid CH3CO2H • Butter (Latin: butyrum)  butyric acid CH3(CH2)2CO2H, from rancid butter Properties more polar & hydrogen bonding: high mp & bp acidic proton: pKa  5 AcOH ( 3 x 109 lbs/yr), aspirin, ibuprofen(항염증제):  479 OrgChem-Chap12

  18. OrgChem-Chap12

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

  20. acryloyl chloride succinic anhydride ethyl acetate N,N-dimethylformamide acetonitrile monosodium glutamate (MSG) • practice:  483, Problem 12.14~15 OrgChem-Chap12

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

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

  24. OrgChem-Chap12

  25. Nitrile or cyano group +NH3 -H2O -H2O 1) 3-pentynenitrile ----  ---nitrile ----oic acid ----ic acid  ---nitrile Benzonitrile  benzoic acid 2) Complex compound  cyano Methyl 4-cyanobenzoate (priority) see p. 490 table 11.3 OrgChem-Chap12

  26. Carboxylate salt carboxylate anion + cation --ic acid cation ---ate Sodium acetate Ammonium 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 OrgChem-Chap12

  27. 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 (CH3CO2CH2CH2CH(CH3)2 : banana odor methyl butanoate (CH3CH2CH2CO2CH3): 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 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 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 CH3CH(CH3)CH2CH2-SH: 3-methyl-1-butanethiol stinky odor, stronger acid, better nucleophile • R-S-R’: sulfides; alkylalkyl sulfide (CH3-S-CH3: dimethyl sulfide) OrgChem-Chap12

  31. OrgChem-Chap12

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

  33. OrgChem-Chap12

  34. Phosphorus: P NH3: amine  nitrogen PH3:phosphine  phosphorus PH3 phosphine  phosphate • phosphoric acid (H3PO4) triphenyl phosphine: PPh3 Dialkyl hydrogen phosphate PH3: phosphine, a toxic gas with bad odor PPh3: good nucleophile & transition metal ligand (RO)2P(O)OH: phosphate, backbone for RNA/DNA phosphatidylcholine: constituent of membranes practice:  491 Problem 12.17~18 OrgChem-Chap12

  35. OrgChem-Chap12

  36. OrgChem-Chap12

  37. OrgChem-Chap12

  38. OrgChem-Chap12

  39. OrgChem-Chap12

  40. 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 O Ethyl 3-oxobutanoate 3-cyano-6-hydroxy-4-pentenal OrgChem-Chap12

  42. OrgChem-Chap12

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

More Related