1-1 Chemistry 121, Winter 2014, LA Tech Introduction to Organic Chemistry and Biochemistry Instructor Dr. Upali Siriwardane (Ph.D. Ohio State) Office: 311 Carson Taylor Hall ; Phone: ; Office Hours: MTW 9:00 am - 11:00 am; TR 9: :00 am & 1:00-2:00 pm. December 20, Test 1 (Chapters 12-13) January 27 Test 2 (Chapters 14-16) February 14 Test 3 (Chapters 17-19) February 26, Test 4 (Chapters 20-22) February 27, 2014, Make Up Exam: Bring Scantron Sheet 882-E Chemistry 121(01) Winter 2014

1-2 Chemistry 121, Winter 2014, LA Tech Chapter 15: Aldehyde and Ketones 15.1 The Carbonyl Group, Compounds Containing a Carbonyl Group, The Aldehyde and Ketone Functional Groups, Nomenclature for Aldehydes, Nomenclature for Ketones, Isomerism for Aldehydes and Ketones, Selected Common Aldehydes and Ketones, Physical Properties of Aldehydes and Ketones, Preparation of Aldehydes and Ketones, Oxidation and Reduction of Aldehydes and Ketones, Reaction of Aldehydes and Ketones with Alcohols, Formaldehyde-Based Polymers, Sulfur-Containing Carbonyl Groups, 492

1-3 Chemistry 121, Winter 2014, LA Tech Carbonyl Group

1-4 Chemistry 121, Winter 2014, LA Tech Simplest Aldehyde

1-5 Chemistry 121, Winter 2014, LA Tech Common Names of Aldehyde and Ketones Aldehydes: Fomaldehyde: HCHO Acetaldehyde: CH 3 CHO Propionaldehyde: CH 3 CH 2 CHO Butyraldehyde: CH 3 CH 2 CH 2 CHO Valeraldehyde: CH 3 CH 2 CH 2 CH 2 CHOKetones: Acetone: CH 3 COCH 3 Methyl ethyl ketone CH 3 CH 2 COCH 3 Butyl propyl ketone CH 3 CH 2 CH 2 CH 2 COCH 2 CH 2 CH 3

1-6 Chemistry 121, Winter 2014, LA Tech IUPAC Nomenclature of Aldehyde and Ketones The IUPAC system deals with functional groups two different ways. Modification of the hydrocarbon name to indicate the presence of a functional group. al aldehyde, -CHO use -al ending. one Ketones -RCOR’ use -one ending.

1-7 Chemistry 121, Winter 2014, LA Tech IUPAC Nomenclature of Aldehyde and Ketones The IUPAC system deals with functional groups two different ways. Modification of the hydrocarbon name to indicate the presence of a functional group. al aldehyde, -CHOuse -al ending. one Ketones -RCOR’ use -one ending.

1-8 Chemistry 121, Winter 2014, LA Tech Example C - C - C - C - CHO Base contains 5 carbon -aldehyde name is pentane -e -al -remove -e and add -al C - C - C - C - CO-C-C Base contains 7 carbon -aldehyde name is heptane -e -one -remove -e and add -one 3-heptanone

1-9 Chemistry 121, Winter 2014, LA Tech Physical Properties of Aldehydes and ketones Aldehyde and ketones can only make dipole-dipole attraction. BP and MP are lower than alcohols, higher than hydrocarbons and ether with comparable carbon numbers

1-10 Chemistry 121, Winter 2014, LA Tech Bonding Characteristics of Aldehydes Ketones Both aldehydes and ketones contain a carbonyl functional group. A carbonyl group is an carbon atom double-bonded to an oxygen atom. The structural representation for a carbonyl group is Carbon-oxygen (C=O) and carbon-carbon (C=C) double bonds differ in a major way. A carbon oxygen double bond is more polar

1-11 Chemistry 121, Winter 2014, LA Tech Physical properties of aldehydes and ketones.

1-12 Chemistry 121, Winter 2014, LA Tech Nomenclature

1-13 Chemistry 121, Winter 2014, LA Tech Name the Aldehyde 2,4-dimethylpentanal

1-14 Chemistry 121, Winter 2014, LA Tech 1. Assign the type of organic compound with following general condensed (structural formula.

1-15 Chemistry 121, Winter 2014, LA Tech 2. Names (common/IUPAC)of following aldehydes and ketones. a) ____________ b) _______________ c) __________________ d) ____________ e) _______________ f) __________________ g) ____________ h) __________________

1-16 Chemistry 121, Winter 2014, LA Tech Nomenclature

1-17 Chemistry 121, Winter 2014, LA Tech 3. Draw the condensed formula of following aldehydes and ketones : a)acetaldehyde/ ethanal b) ethyl methyl ketone c) 3-methyl-2- pentanone d) isopropyl methyl ketone e) 2- methylbutanal f) 5-methyl-3- hexanone g) benzophenone h) acetophenone

1-18 Chemistry 121, Winter 2014, LA Tech Addition reactions of als & ones Hemiacetal or hemiketal formation

1-19 Chemistry 121, Winter 2014, LA Tech Hemiacetal form of cyclic sugars

1-20 Chemistry 121, Winter 2014, LA Tech 4. Identify each of the following compounds as a hemiacetal, hemiketal, acetal, or ketal: a) ____________ b) _______________ c) __________________ d) ____________ e) _______________ f) __________________

1-21 Chemistry 121, Winter 2014, LA Tech Important Aldehydes Methanal or formaldehyde Ethanal or acetaldehyde 2-Propanone or acetone 2-Butanone or methyl ethyl ketone Oil of almonds or benzaldehyde Oil of Cinnamon or cinnamaldehyde Oil of vanilla beans or vanillin Mushroom flavoring or 2-octanone Oil of lemongrass or citral:

1-22 Chemistry 121, Winter 2014, LA Tech Bakelite

1-23 Chemistry 121, Winter 2014, LA Tech Preapration of Aldehydes: Partial oxidation of primary alcohols with H 2 CrO 4 :

1-24 Chemistry 121, Winter 2014, LA Tech Preapration of ketones: Oxidation of secondary alcohols with KMnO 4, or H 2 CrO 4

1-25 Chemistry 121, Winter 2014, LA Tech Oxidation of alcohol

1-26 Chemistry 121, Winter 2014, LA Tech Oxidation of alcohol

1-27 Chemistry 121, Winter 2014, LA Tech 5) Which alcohol would you oxidize to produce each of the following compounds? a) b) c) d)

1-28 Chemistry 121, Winter 2014, LA Tech Oxidation of Alcohols to oxidize a 1° alcohol to an aldehyde, use PCC PCC oxidation of geraniol gives geranial Tertiary alcohols are not oxidized by either of these reagents; they are resistant to oxidation

1-29 Chemistry 121, Winter 2014, LA Tech 6) Preparation of adehydes and ketones a)Control oxidation of 1ry alcohol b) Complete oxidation of 1 ry alcohol

1-30 Chemistry 121, Winter 2014, LA Tech 6) Preparation of adehydes and ketones c) Oxidation of 2 ry alcohol d) Oxidation of 3 ry alcohol No Reaction

1-31 Chemistry 121, Winter 2014, LA Tech Chemical Reactions of Aldehydes and Ketone 1) Combustion: Alkenes are very flammable and the combustion products are carbon dioxide and water. 2) Addition Reactions: Atoms or group of atoms are added to each a carbon oxygen double bond. Two different reactants are involved. a) hemi-acetal or hemi-ketal formation : Addition of Alcohols: -OR group of the R-OH is added to the C atom and H of the ROH is added to O atom. b) Aacetal or ketal formation : Another or second ROH is reacted in a substitution reaction to replace the H atom of the -OH group of the hemi-acetal or hemi-ketal and water molecule is produced. O: both reactants (H-X (X= Cl, OH)) and the alkene need to be asymmetric 3) Oxidation Reactions: only aldehydes are oxidized to carboxylic acids. 4) Reduction Reactions: both aldehydes and ketones are reduced to alcohols by taking H from the reducing agents.

1-32 Chemistry 121, Winter 2014, LA Tech Reduction of als & ones compounds to alcohols:

1-33 Chemistry 121, Winter 2014, LA Tech Aldehyde and Ketone Reduction: To alcohols

1-34 Chemistry 121, Winter 2014, LA Tech 7) Complete the following reductions of aldehyde and ketones and identify the type of alcohols (1ry, 2ry and 3ry) produced. d)

1-35 Chemistry 121, Winter 2014, LA Tech Reduction of als & ones compounds to alcohols:

1-36 Chemistry 121, Winter 2014, LA Tech Addition reactions of als & ones Hemiacetal or hemiketal formation

1-37 Chemistry 121, Winter 2014, LA Tech Addition reactions of als & ones Hemiacetal or hemiketal formation

1-38 Chemistry 121, Winter 2014, LA Tech Hemiacetal form of cyclic sugars

1-39 Chemistry 121, Winter 2014, LA Tech Formation of Acetals and Ketals.

1-40 Chemistry 121, Winter 2014, LA Tech 8) Complete the following formation reactions hemiacetal, hemiketal, acetal, or ketal:

1-41 Chemistry 121, Winter 2014, LA Tech Chemical Reactions Oxidation of aldehyde. Benedict's Test for aldehydes:

1-42 Chemistry 121, Winter 2014, LA Tech Test for Urine Glucose: Benedict’s Test

1-43 Chemistry 121, Winter 2014, LA Tech Oxidation of aldehyde. The commercial manufacture of silver mirrors uses a similar process. Tollen's Test:

1-44 Chemistry 121, Winter 2014, LA Tech 9) Complete reactions of following aldehydes and ketones a) Tollen’s Reagent: Silver mirror test: b) Benedict's test:

1-45 Chemistry 121, Winter 2014, LA Tech 9) Complete reactions of following aldehydes and ketones c) Oxidation of aldehyde d) Cyclic hemi-acetal formation

1-46 Chemistry 121, Winter 2014, LA Tech Addition of HCN and H 2 O

1-47 Chemistry 121, Winter 2014, LA Tech Aldol Condensation In biological systems this reaction is catalysed by an enzyme named aldolase.

1-48 Chemistry 121, Winter 2014, LA Tech Keto & Enol tautomers keto form enol from

1-49 Chemistry 121, Winter 2014, LA Tech Keto & Enol tautomers in sugars aldehyde enol ketone

1-50 Chemistry 121, Winter 2014, LA Tech Addition reactions of als & ones Hemiacetal or hemiketal formation

1-51 Chemistry 121, Winter 2014, LA Tech Formation of Acetals and Ketals.

1-52 Chemistry 121, Winter 2014, LA Tech Hemiacetal form of cyclic sugars