New version page

Functional Derivatives of Carboxylic Acids

Upgrade to remove ads

This preview shows page 1-2-3-18-19-36-37-38 out of 38 pages.

Save
View Full Document
Premium Document
Do you want full access? Go Premium and unlock all 38 pages.
Access to all documents
Download any document
Ad free experience
Premium Document
Do you want full access? Go Premium and unlock all 38 pages.
Access to all documents
Download any document
Ad free experience
Premium Document
Do you want full access? Go Premium and unlock all 38 pages.
Access to all documents
Download any document
Ad free experience
Premium Document
Do you want full access? Go Premium and unlock all 38 pages.
Access to all documents
Download any document
Ad free experience
Premium Document
Do you want full access? Go Premium and unlock all 38 pages.
Access to all documents
Download any document
Ad free experience
Premium Document
Do you want full access? Go Premium and unlock all 38 pages.
Access to all documents
Download any document
Ad free experience
Premium Document
Do you want full access? Go Premium and unlock all 38 pages.
Access to all documents
Download any document
Ad free experience
Premium Document
Do you want full access? Go Premium and unlock all 38 pages.
Access to all documents
Download any document
Ad free experience

Upgrade to remove ads
Unformatted text preview:

PowerPoint PresentationSlide 2Slide 3Slide 4Slide 5Slide 6Slide 7Slide 8Slide 9Slide 10Slide 11Slide 12Slide 13Slide 14Slide 15Slide 16Slide 17Slide 18Slide 19Slide 20Slide 21Slide 22Slide 23Slide 24Slide 25Slide 26Slide 27Slide 28Slide 29Slide 30Slide 31Slide 32Slide 33Slide 34Slide 35Slide 36Slide 37Slide 38Functional Derivatives of Carboxylic AcidsR CNH2OR COORCClOR COR'OCORacid chlorideanhydrideamideesterR may be H or ArNomenclature: the functional derivatives’ names are derived from the common or IUPAC names of the corresponding carboxylic acids.Acid chlorides: change –ic acid to –yl chlorideAnhydrides: change acid to anhydrideCClOCH3CH2CH2COClbutanoyl chloridebutyryl chloridebenzoyl chlorideH3C COH3C COOOOOOOOethanoic anhydrideacetic anhydridephthalic anhydridemaleic anhydrideAmides: change –ic acid (common name) to –amide -oic acid (IUPAC) to –amideEsters: change –ic acid to –ate preceded by the name of the alcohol groupCNH2OCH3CH2CH2CONH2butanamidebutyramidebenzamideCO CH2CH3Oethyl benzoateCH3CH2CH2COO CH3methyl butanoatemethyl butyrateNucleophilic acyl substitution:R CZOR CWO+ :ZR C WOZ+ :W-W = -OH, -Cl, -OOCR, -NH2, -OR'R CO= "acyl" groupR CZOR CWO+ :ZR C WOZ+ :WR C WOZRDSMechanism: Nucleophilic Acyl Substitution1)2)R CZOR CWOH+ :ZHR C WOHZH+ HW + H+R C WOHZHRDSR CWOHR CWO+ H+Mechanism: nucleophilic acyl substitution, acid catalyzed1)2)3)nucleophilic acyl substitution vs nucleophilic addition to carbonylaldehydes & ketones – nucleophilic additionfunctional deriv. of carboxylic acids – nucleophilic acyl substitutionRCZORCWO+ :ZR C WOZ+ :W-W = -OH, -Cl, -OOCR, -NH2, -OR'R CR'O+ :ZR C R'OZYR C R'OYZAcid ChloridesSyntheses: SOCl2RCOOH + PCl3  RCOCl PCl5COHO+ SOCl2CClObenzoic acid benzoyl chlorideOHO+ PCl3ClO3-methylbutanoic acidisovaleric acid3-methylbutanoyl chlorideisovaleryl chlorideAcid chlorides, reactions:1. Conversion into acids and derivatives:a) hydrolysisb) ammonolysisc) alcoholysis2. Friedel-Crafts acylation3. Coupling with lithium dialkylcopper4. Reductionacid chlorides: conversion into acids and other derivativesClOH2OOHOHydrolysisisovaleryl chloride3-methylbutanoyl chlorideisovaleric acid3-methylbutanoic acidAmmonolysis CH3CH2CClONH3CH3CH2CNH2Opropionyl chloridepropanoyl chloridepropionamidepropanamideAlcoholysisCOClCH3CH2OHCOOCH2CH3benzoyl chlorideethyl benzoateSchotten-Baumann technique – aromatic acid chlorides are less reactive than aliphatic acid chlorides. In order to speed up the reactions of aromatic acid chlorides, bases such as NaOH or pyridine are often added to the reaction mixture.O2NO2NCOClpyridineCH3CH2CH2OHO2NO2NCOOCH2CH2CH33,5-dinitrobenzoyl chloriden-propyl-3,5-dinitrobenzoateacid chlorides: Friedel-Crafts acylationR COCl+ ArHAlCl3R C ArO+ HClphenoneCH3CH2CH2COClCH3+toluenebutyryl chlorideAlCl3CH3CH2CH2COCH3+ ortho-p-methylbutyrophenoneCH3CH2CH2COClbutyryl chloride+NO2AlCl3No reactonacid chlorides: coupling with lithium dialkylcopper R COCl+ R'2CuLiR C R'OketoneCOCl+ (CH3CH2CH2)2CuLiC CH2CH2CH3Obenzoyl chloridelithium di-n-propylcopperbutyrophenoneCClO+2CuLiO2,4-dimethyl-3-pentanoneisobutyryl chloridelithium diisopropylcopperacid chlorides: reduction to aldehydesR CClOLiAlH(t-BuO)3R CHOCOClCOHLiAlH(t-BuO)3mechanism, nucleophilic acyl substitution by hydride :H-R CClO1)+ :HR C ClOHRDS2)R C ClOHR CHO+ ClAnhydrides, syntheses:Buy the ones you want!Anhydrides, reactions:1) Conversion into carboxylic acids and derivatives.a) hydrolysisb) ammonolysisc) alcoholysis2) Friedel-Crafts acylationOOOphthalic anhydride+ H2OCOOHCOOH(CH3CO)2O+ NH3CH3CNH2OCH3CONH4O+acetic anhydridephthalic acidacetamideOOO+ CH3CH2OHsuccinic anhydrideCH2COCH2CH3OCH2COHOethyl hydrogen succinateammonium acetate2) anhydrides, Friedel-Crafts acylation.(RCO)2O + ArHAlCl3R COHO+R C ArOphenone(CH3CO)2O+CH3AlCl3H3C COCH3+ CH3CO2Hacetic anhydridetoluene p-methylacetophenoneOOOphthalic anhydride+AlCl3COCOOHo-benzoylbenzoic acidAmides, synthesis:Indirectly via acid chlorides.R COHOSOCl2R CClONH3R CNH2O[ carboxylic acids form ammonium salts when reacted directly with ammonia ]CH3CH2CH2CO2H CH3CH2CH2COClPCl3NH3CH3CH2CH2CONH2butyric acid butyryl chloridebutyramideCOOHPCl5CClONH3CNH2Obenzoic acid benzoyl chloridebenzamideAmides, reactions.1) Hydrolysis.R CNH2OH2O, H+ or OH-heatR COHOCH3CHCH2CCH3NH2Oisovaleramide+ H2OH+heatCH3CHCH2CCH3OHOisovaleric acidHN CHCORHN CHCROHN CHCROHN CHCROHN CHCROHN CHCROproteins are polyaminoacidsH2N CHCROHOaminoacids"peptide bond"hydrolysisWool, hair, silk, spider web: fibrous proteins.Silk is an extremely strong, thin, lightweight fiber, perfect for making sheer stockings for women as well as parachutes. It is made by the silkworm, a domesticated moth larva raised in Japan and China. During World War II a substitute material was needed and developed by DuPont – Nylon-66, a synthetic polyamide of adipic acid and hexamethylenediamine:C(CH2)4CO OCladipoyl chloride+ H2N (CH2)6NH2hexamethylenediamineC(CH2)4CO ONH (CH2)6NHC(CH2)4CO ONH (CH2)6NHNylon-66ClEsters, syntheses:1) From acidsRCO2H + R’OH, H+ RCO2R’ + H2O2) From acid chlorides and anhydridesRCOCl + R’OH RCO2R’ + HCl3) From esters (transesterification)RCO2R’ + R”OH, H+ RCO2R” + R’OHRCO2R’ + R”ONa RCO2R” + R’ONaEsters often have “fruity” or “floral” odors:isopentyl acetate banana oiln-pentyl butyrate apricotisopentyl isovalerate appleethyl butyrate peachethyl heptanoate cognacethyl nonate flower bouquetethyl laurate tuberosemethyl butyrate pineappleoctyl acetate orangeCOOHisovaleric acid+ CH3CH2OHethyl alcoholH+COOethyl isovalerate+ H2OSOCl2COClisovaleryl chloride+ CH3CH2OHethyl alcoholCOOethyl isovalerate+ HCl“Direct” esterification is reversible and requires use of LeChatelier’s principle to shift the equilibrium towards the products. “Indirect” is non-reversible.In transesterification, an ester is made from another ester by exchanging the alcohol function.CH3CH2CH2COOCH3methyl butanoate+isopropyl alcoholH+CH3CH2CH2COOisopropyl butanoate+ CH3OHCHCH3CH3CHCH3HOCH3CH3CH2CH2COOCH3methyl butanoate+CH2ONabenzyl alcoholCH3CH2CH2COO+CH2CH3ONabenzyl butanoateEsters, reactions:1) Conversion into acids and derivativesa) hydrolysisb) ammonolysisc) alcoholysis2) Reaction with Grignard reagents3) Reductiona)


Download Functional Derivatives of Carboxylic Acids
Our administrator received your request to download this document. We will send you the file to your email shortly.
Loading Unlocking...
Login

Join to view Functional Derivatives of Carboxylic Acids and access 3M+ class-specific study document.

or
We will never post anything without your permission.
Don't have an account?
Sign Up

Join to view Functional Derivatives of Carboxylic Acids 2 2 and access 3M+ class-specific study document.

or

By creating an account you agree to our Privacy Policy and Terms Of Use

Already a member?