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Lecture 14 Carbonyl Chemistry

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Lecture 14 Carbonyl Chemistry Lecture 14 Carbonyl Chemistry - O O C C + A B A B March 7, 2019 Chemistry 328N A “loose end” Chemistry 328N A word of caution regarding acylation reactions O + C = HC O HCl H Cl Does not exist!! Chemistry 328N Gatterman-Koch Reaction O = HCl C O H C + Cl O CO, HCl C H AlCl3, CuCl Chemistry 328N Vilsmeier Reaction O O C H 3 C P O C l 3 H + C N H C H 3 H 2 P d / C C H 3 Chemistry 328N Resonance Description of Carbonyl Group •• – • •• O• •O• C C + nucleophiles attack carbon; electrophiles attack oxygen Chemistry 328N Nomenclature-Aldehydes ⚫ IUPAC names: select as the parent alkane the longest chain of carbon atoms that contains the carbonyl group..subtract e and add al – because the carbonyl group of the aldehyde must be on carbon 1, there is no need to give it a number ⚫ For unsaturated aldehydes, show the presence of the C=C by changing -an- to -en- – the location of the suffix determines the numbering pattern Chemistry 328N IUPAC Nomenclature-Aldehydes O Methane Methanal HCH O CH3 O 5 4 3 2 1 4 3 2 1 CH3 CH2 CH2 CH2 CH CH3 CHCH 2 CH Pentane Pentanal 3-Methylbutanal O O 3 2 1 7 5 3 1 CH2 =CHCH H 8 6 4 2 2-Propenal (2E)-3,7-Dimethyl-2,6-octadienal (Acrolein) (Geranial) Chemistry 328N Formaldehyde ⚫ “Formalin” is an aqueous solution of a mixture of formaledyde derived species ⚫ Used for emblaming and preservation of tissue samples, bugs, etc. ⚫ Widely used in melamine resins for plywood, flooring, etc… ⚫ Naturally occuring at 0.1mm in blood derived from metbolism of amino acids ⚫ Toxicity is an issue and level set at 0.016ppm in air. Thirty ml ogf Chemistry 328N Nomenclature-Ketones ⚫ IUPAC names: – select as the parent alkane the longest chain that contains the carbonyl group, – number to give C=O the smaller number and then subtract e and add one 7 1 O O CH3 6 O 1 2 3 4 5 6 CH3 CCH3 CH CH CCH CHCH 5 2 3 2 2 3 4 3 Propanone 5-Methyl-3-hexanone Bicyclo[2.2.1]-2- (Acetone) heptanone Chemistry 328N IUPAC Nomenclature of Ketones O O CH3CH2CCH2CH2CH2CH3 CH3CHCH2CCH3 3-heptanone CH3 4-methyl-2-pentanone H3C O 4-methylcyclohexanone Chemistry 328N IUPAC Nomenclature of Ketones O O CH3CHCH2CCH3 CH3CH2CCH2CH2CH3 CH3 3-hexanone 4-methyl-2-pentanone O O H CH3CH2CCH2CH2CH3 O ethyl propyl ketone (trivial) 4-oxohexanal Chemistry 328N Trivial Nomenclature of Ketones O O CH3CCH2CH3 CH2CCH2CH3 Methyl ethyl ketone benzyl ethyl ketone O H2C CHCCH CH2 divinyl ketone Chemistry 328N Order of Precedence (Pecking order) ⚫ For compounds that contain more than one functional group indicated by a suffix Functional Suffix if Higher Prefix if Lower Group in Precedence in Precedence -CO 2 H -oic acid -CHO -al oxo- C=O -one oxo- -OH -ol hydroxy- Precedene -NH 2 -amine amino- -SH -thiol mercapto- Chemistry 328N Many aldehydes and ketones occur naturally O O 2-heptanone trans-2-hexenal (component of alarm (alarm pheromone pheromone of bees) of myrmicine ant) Testosterone Chemistry 328N Wild Kopi Luwak, the World’s Most Exclusive Coffee Cock Roach Sex Pheromone Civit Cat $416/pound on AmazonCivitone Cortisone Chemistry 328N Synthesis of Aldehydes and Ketones A number of • from alkenes reactions already • by ozonolysis (p271) studied provide efficient synthetic • from alkynes routes to • by hydration (via enol) aldehydes and ketones. • from arenes • via Friedel-Crafts acylation Chemistry 328N Reaction Theme ⚫ The most common reaction of a carbonyl group is addition of a nucleophile to form a tetrahedral addition compound - R O Nu - + C O Nu C R R R Here it is an acid or electrophile Tetrahedral carbonyl addition compound Chemistry 328N Carbon Nucleophiles ⚫ Addition of carbon nucleophiles is one of the most important types of nucleophilic additions to a C=O group; a new carbon-carbon bond is formed in the process!!!! RMgX RLi RC C - - C N A Grignard An organolithium An anion of a Cyanide reagent reagent terminal alkyne ion ⚫ We will study the addition of these carbon nucleophiles Chemistry 328N Victor Grignard Shared Nobel “student” of Prize with Philippe Barbier Sabatier in 1912 Chemistry 328N Grignard Reagents ⚫ Given the difference in electronegativity between carbon and magnesium, the C-Mg bond is polar covalent, with C - and Mg + – Grignard reagents behave like a carbanions ⚫ Carbanion: an anion in which carbon has an unshared pair of electrons and bears a negative charge – a carbanions are good nucleophiles and add efficiently to the carbonyl group of aldehydes and ketones Chemistry 328N Grignard Reagents X = Cl, Br, I Diethyl ether Tetrahydrofuran Et2O THF Chemistry 328N Crystal Structure of CH3CH2MgBr Br Mg O O L.J. Guggenberger and R.E. Randle , J. Amer. Chem. Soc. 90(20) 5357 (1968) Chemistry 328N Grignard Reagents ⚫ Addition of a Grignard reagent to + formaldehyde followed by H3O gives a 1° alcohol H H H - + + +2 - + H3O CH CH MgBr C O CH3CH2 C O MgBr CH3CH2 C OH + Mg 3 2 THF H H dil. H ⚫ This sequence (mechanism) is general and important! Chemistry 328N Grignard Reagents ⚫ Addition to any other RCHO gives a 2° alcohol - + + +2 - + H3O CH CH MgBr C O CH3CH2 C O MgBr CH3CH2 C OH + Mg 3 2 THF H H dil. H • You may change decorations at will…read pages 567-573 – but, be careful of acidic functions like -OH Chemistry 328N Grignard Reagents ⚫ Addition to a ketone gives a 3° alcohol CH3 CH3 CH3 CH2 CH2 CH2 CH2 CH2 CH2 - + + +2 - + CH CH C O MgBr H3O + Mg CH3CH2 MgBr C O 3 2 CH3CH2 C OH THF dil. CH3 CH3 CH3 ⚫ Please try this with other Grignard reagents and other ketones Chemistry 328N Grignard Reactions CH3 CH3 CH3 CH2 CH2 CH2 H + H H CH - + H O +2 - + CH2 CH CH C 2O - MgBr+ 3 + CH2 + Mg+2 CH3CH2 M- gBr + C O 3 2 H3O+ CH3CH2 C OH - + C O CH3CH2 C O- MgB+r H O CH3CH2 C OH ++M2 g CH3CH2 MgBr C OTHF CH3CH2 C O MgBr 3 dil. CH CH C OH + Mg CH3CH2 MgBr H THF H 3 2 H H THF H di dil. l. H CH3 CH3 CH3 Chemistry 328N Grignard reagents also react with esters R' R' •• + OCH3 diethyl – •• •• R C ether R C OCH •• 3 • • + MgX O• •O• MgX •• • •• – but species formed is unstable and dissociates under the reaction conditions to form a ketone Chemistry 328N Grignard reagents react with esters R' R' •• + OCH3 diethyl – •• •• R C ether R C OCH •• 3 • • + MgX O• •O• MgX •• • •• – this ketone then goes –CH3OMgX on to react with a second mole of the R R' Grignard reagent to C give a tertiary alcohol O• •• Chemistry 328N Example O 2 CH3MgBr + (CH3)2CHCOCH3 1. diethyl ether + 2. H3O Two of the groups OH attached to the (CH ) CHCCH tertiary carbon 3 2 3 come from the CH3 Grignard reagent (73%) Chemistry 328N Grignard reagents react with: formaldehyde to give primary alcohols aldehydes to give secondary alcohols ketones to give tertiary alcohols esters to give tertiary alcohols CO2 to give acids O epoxides give primary alcohols Chemistry 328N Grignard Reagents ⚫ Problem: 2-phenyl-2-butanol can be synthesized by three different combinations of a Grignard reagent and a ketone. Show each combination OH C-CH 2 CH3 CH3 Chemistry 328N Practice Problem 1. Starting from benzene, write a synthetic path to the structures below. You are free to use any reagents or reactants you choose, but you must start with benzene. H COOH C O H Br Cl Chemistry 328N Oxygen Nucleophiles O OR" + 2R"OH C R C R' + H2O R R' OR" Chemistry 328N Alcohols React with Aldehydes and Ketones in two steps…first R • C O • •• R' R"OH R •• •• Product is called R"O C O H •• •• a hemiacetal. R' Chemistry 328N Hemiacetal reacts further in acid to yield an acetal R •• •• R"O C O R This product is •• •• called an acetal. R' ROH, H+ R •• •• R"O C O H This hemiacetal •• •• reacts further. R' Chemistry 328N Example O + CH 2CH3CH2OH HCl CH(OCH2CH3)2 + H2O Benzaldehyde diethyl acetal Chemistry 328N Diols Form Cyclic Acetals O CH3(CH2)5CH + HOCH2CH2OH benzene acid catalyst H2C CH2 O O + H2O C H (CH2)5CH3 Chemistry 328N Mechanism of Acetal Formation + H H •• • H O• H O • • + R R H •• • C O• H O • + • R Chemistry 328N Mechanism •• + C O H •• + C O •• H Resonance stabilized cation Chemistry 328N Mechanism R •• • O • + C O • • •• H H Chemistry 328N Mechanism R •• •• O C O• + H H Chemistry 328N Mechanism R •• •• O C O• + H H •• O R •• H Chemistry 328N Mechanism R •• •• O C O• Hemi acetal ! •• H H + H •• • + R O• O R •• H H Catalyst regenerated! Chemistry 328N Mechanism of Acetal Formation Second stage is hemiacetal-to-acetal conversion involves carbocation chemistry Chemistry 328N Hemiacetal-to-acetal Stage H R •• •• • O C O• H O • •• + H R These are not separate reactions… this is all one big equilibrium Chemistry 328N Hemiacetal-to-acetal Stage R H •• •• O C O + •• H Chemistry 328N Hemiacetal-to-acetal Stage R H •• O C+ • •• •• •O H R + Here is the water! O C •• Chemistry 328N Hemiacetal-to-acetal Stage R R •• •• O C+ •O •• • H Chemistry 328N Hemiacetal-to-acetal Stage R R •• •• O C O + R •• •• H •O H Chemistry 328N Hemiacetal-to-acetal Stage R R •• •• O C O R •• •• •• H O + The acetal H Regeneration of catalyst Chemistry 328N Note that EVERY step is an equilibrium Therefore, the reaction can be pushed forward or backward by appropriate choice of conditions The forward reaction is synthesis The backward reaction is hydrolysis Chemistry 328N Hydrolysis of Acetals OR" O + R C R' + H2O C 2R"OH R R' OR" mechanism: reverse of acetal formation …hemiacetal is intermediate.
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