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Angelo State University Angelo State University 1
The Carbonyl Group
Chapter 4 Notes
The Carbonyl Group
•The carbonyl group (C=O) is found in aldehydes , ketones , and many other organic functional groups. • The carbon and oxygen in the carbonyl group are sp 2 -hybridized, with bond angles of 120°.
the carbony l group
•In ketones , two carbon groups are attached to the carbonyl carbon, while in aldehydes at least one hydrogen is attached to the carbon.
O C RH
O C RR'
Functional Groups Containing Carbonyls
O C RR'
O C RH O O R' C O C RO O C RN
O C RO HC RO
carboxylic acid ester acid anhydride
etc.S. good solvent for most organic compounds. and is also found in apricots and peaches. solvent for coatings such as fingernail polish and enamel paints. sweating. and embalm cadavers. called formalin . used to preserve biological specimens. reduced blood pressure. and is also soluble in water. 2-Butanone (Methyl ethyl ketone. and helps to preserve smoked meats by killing bacteria. leading to nausea. etc. present in wood smoke. sterilize instruments. consuming large quantities of ethanol causes acetaldehyde to build up in bloodstream faster than it can be consumed in the liver to make other products. 35-40% solution in water. CH3 O C H CH 3 O C Benzaldehyde Causes the odor of almonds and cherries. MEK) Common industrial solvent CH 2 CH 3 6 .. O C 2-Propanone (Acetone) 1 billion pounds used annually in U. O C CH3 CH 3 H Ethanal (Acetaldehy de) Product of oxidation of ethanol in the liver.Chapter 4 Notes Nomenclature of Aldehydes and Ketones 5 Some Common Aldehydes and Ketones O C H H Methanal (Formaldehyde) Gas at room temperature.
the carbonyl carbon should have the lowest possible number).Chapter 4 Notes Nomenclature of Aldehydes • Select the longest carbon chain carbonyl carbon . O O CCH CH 3 CH 2 CH 2 CCH 3 3 CH 3 CH 2 CCH CH 2 2 CH 3 CH 2 CH 3 8 CH 2 .. containing the •The -e ending of the parent alkane name is replaced by the suffix -al . • The carbonyl carbon is always numbered “1. • Name the substituents attached to the chain in the usual way. O O CH CH 3 CH 2 CH 2 CH CH 3 CH 2 CH CH 2 CH 3 7 Nomenclature of Ketones • Select the longest carbon chain carbonyl carbon .) • Name the substituents attached to the chain in the usual way. containing the •The -e ending of the parent alkane name is replaced by the suffix -one . • Number the chain starting with the end closest to the ketone group (i.” (It is not necessary to include the number in the name.e.
Chapter 4 Notes Examples: Naming Aldehydes and Ketones • Name the following compounds: Br CH 3 CHCH 2 O CH H O C CH 2 CH CH 3 CH 3 CH CH 3 CH 3 O 3 O CH 3 C CHCH 2 CH 3 CH 3 CH CH C CH CH 3 CH 2 CH 3 9 Other Nomenclature Rules • In cyclic ketones. (The carbon to which the aldehyde group is attached is carbon “1”). tri one. • Aromatic aldehydes (containing an aldehyde group directly attached to a benzene ring) are named after the parent compound benzaldehyde . • Molecules with more than one ketone group are named by preceding the suffix with a counting prefix ( di one. 10 .). position numbers must be used for each ketone group. etc. The numbering continues clockwise or counterclockwise to give the lowest number for the next substituent. this does not need to be included in the name. the carbonyl group is always numbered “1”.
4.Chapter 4 Notes Examples: Naming Aldehydes and Ketones • Name the following compounds: OO CH 3 CH 3 O O 3 CCCH O C H CH 3 O C H Br CH 3 11 Examples: Naming Aldehydes and Ketones • Draw structural formulas for the following molecules: – 3-ethyl-2-pentanone – 2.6-trimethylheptanal – 3-ethylcyclopentanone – 4-chloro-2-phenylpentanal – para -nitrobenzaldehyde – 3-ethyl-2-butanone (what’s name?) wrong with this 12 .
but these attractions are not as strong as those that result from hydrogen-bonding. dO C d+ • This creates weak attractive forces between carbonyl compounds.Chapter 4 Notes Physical Properties of Aldehydes and Ketones 13 The Polarity of the Carbonyl Group • Carbonyl compounds are polar. containing a dipole along the carbon-oxygen double bond. d+ CO dd+ CO dd+ CO d- 14 .
d+ HO dd+ H d. – Hydrocarbons are nonpolar. – Aldehydes and ketones are polar. aldehydes and ketones do not form hydrogen bonds with themselves . but they can hydrogen-bond to water through the carbonyl oxygen.O C d+ Od R R' R C+ d R' 16 . and have low boiling points.Chapter 4 Notes The Polarity of the Carbonyl Group • Since there is no hydrogen on the carbonyl oxygen. and have high boiling points. water solubility decreases as the size of the molecule increases. • Aldehydes and ketones therefore have boiling points that are in between those of alcohols and hydrocarbons of the same molecular weight: – Alcohols form hydrogen bonds. but they are not as polar as molecules which can hydrogen bond. • Low-molecular weight aldehydes and ketones are water-soluble. so they have higher boiling points than hydrocarbons. 15 Physical Properties of Aldehydes and Ketones • Carbonyl compounds cannot hydrogen-bond to each other.
Chapter 4 Notes Physical Properties of Aldehydes and Ketones Boiling Points: Alcohols Aldehydes/Ketones Ethers Alkanes Name butane propanal acetone Water Solubility: Alcohols Aldehydes/Ketones Ethers Alkanes Molecular Boiling Solubility weight point in water 58 g/mol 58 g/mol 58 g/mol 0°C 49°C 56°C 97°C Insoluble Soluble Soluble Soluble 17 1-propanol 60 g/mol Examples: Predicting Boiling Points • Arrange the following compounds in order of increasing boiling point: – 2-pentanone – 2-methylpentane –2-pentanol 18 .
which are polyhydroxy aldehydes and ketones . the metabolism of glucose is a major source of energy for living organisms CH 2 OH Fructose Another important carbohydrate. syrups. a major component of corn syrup.Chapter 4 Notes Some Important Aldehydes and Ketones 19 Important Aldehydes and Ketones HO C H HO H H COH C C C H OH OH HO H H CH 2 OH CO C C C H OH OH CH 2 OH Glucose One of the most important of the carbohydrates . and preserves. in combination with glucose it forms the disaccharide sucrose . found in honey. 20 .
also present in the odor of many fruits and dairy products. but can cause convulsions and respiratory collapse in larger doses. fades as the dead skin cells slough off. and as an organic solvent. reacts with dead. and is also responsible for the odor of blue cheese. it appears to selectively stimulate cold sensors. outer skin cells to produce a darker color. It also stimulates the respiratory systems and inspires deep breathing. Acetophenone Used in perfurmery.Chapter 4 Notes Important Aldehydes and Ketones OO HOCH 2 CCH 2 OH 2-Heptanone Found in oil of clove. Camphor is a counter-irritant (produces a superficial inflammation to reduce deeper inflammation) and antipruritic (anti-itching) medication. O CH 3 O O CH3 H HO HO Vanillin flavoring in Vanilla beans Zingerone The pungent. Dihydroxyacetone Active ingredient in "bronzers" that provide fake suntan coloration. hot component of ginger 21 O CH 3 CH3 CH 3 CH3 O Camphor Isolated by steam distillation from the camphor tree of China and Japan. also used in the synthesis of some pharmeceuticals CH 3 O CH 3 CHCH Menthone 3 22 .
spinach. Essential for blood clotting. where it is produced by decomposing sucrose O Methyl 2-pyridyl ketone Found in the odor of popcorn CH 3 O N O Vitamin K 1 A fat soluble vitamin btained from green leafy vegetables. used as an insect repellant 23 O HO O 3-( para -Hydroxyphenyl)2-butanone Responsible for the odor of ripe raspberries. has a carminative action (releases hydrogen sulfide. 5 H O Citronellal Found in citronella oil. the acrid smell of this compound is obvious during barbeques. and hydrogen from the intestine) Hyacinthin Found in hyacinth CH 3 O H 2-Methylundecanal One of the first of the synthetic perfumes. cauliflower. It also contributes to the taste of caramel. cabbage.Chapter 4 Notes O O H H Cinnamaldehyde The flavoring in oil of cinnamon. 24 . obtained by steam distillation from the bark of the cinnamon tree. kale. H Acrolein Produced from the breakdown of triglycerides in meat during cooking. pork liver. introduced by Coco Chanel in 1921 as Chanel No. also made by intestinal bacteria. methane.
O O OH HO OH Humulone A component of hop resin. oil of violets). gives butter its characteristic flavor. Butanedione A volatile yellow liquid compound with the odor of cheese. and sun-dried hay. a viscous yellow material obtained from the blossoms of the female hop plant (Humulus lupulus ). 25 A Few Steroids CH 3 CH 3 OH Steroi nucleu d s O O CH 3 CH 3 C CH 3 Testosterone A male sex hormone H OH C C CH 3 O Progesterone A female sex hormone O Norethynodrel Active ingredient in birth-control pills 26 .Chapter 4 Notes O OO Ionone Responsible for the odor of freshly picked raspberries. violets (and the extract. it adds to the bitter taste of some beers. It also contributes to the odor of armpits and unwashed feet by the action of bacteria which ferment the compounds in perspiration.
Chapter 4 Notes Reactions of Aldehydes and Ketones 27 Oxidation of Alcohols to Produce Carbonyls • Aldehydes. which are not further oxidized: H RC R' 2° alcohol O OH C [O] RR' ketone 28 . like primary alcohols. can be oxidized to produce carboxylic acids: H RC H 1° alcohol O OH C [O] [O] O C ROH carboxylic acid RH aldehyde • Secondary alcohols can be oxidized to produce ketones.
Chapter 4 Notes Examples: Oxidation Reactions • Complete the following reactions: O C H [O] CH 3 CH 3 CHCH 2 O CH 3 CCH O C H [O ] 3 [O ] 29 Examples: Oxidation Reactions • Complete the following reactions: CH 3 CH 3 CHCH 2 OH CH CH 3 [O] OH [O ] 30 .
and the silver ions are reduced to solid silver.” • Ketones are not oxidized.Chapter 4 Notes Oxidation of Aldehydes: The Tollens' Test • Tollens’ reagent is a mild oxidizing agent composed of silver ions in an aqueous basic solution of ammonia. so no silver mirror forms. O RC H RC 2 Ag(NH 3 )2 (OH) 2 ++++ aldehyde Tollen's reagent silver O RC R NR 2 Ag(NH 3 )2 (OH) 2 + 31 O O . which coats the bottom of the test tube with a “silver mirror.NH 4+ a carboxylate salt 3NH 3 2Ag H 2O ketone Tollen's reagent Examples: The Tollens ’ Tes t • What observations would be made in the following reactions? O CH 3 CH 2 O CH 3 C CH 3 O C H Tollen's reagent Tollen's reagent C H Tollen's reagent Tollen's Unknown silver ppt reagen t 32 . • Aldehydes are oxidized to carboxylate salts (since the solution is basic).
Chapter 4 Notes Hydrogenation of Aldehydes and Ketones • Hydrogenation of aldehydes and ketones with hydrogen gas and a platinum catalyst produces alcohols: OOH RCH RCH an aldehyde + H2 Pt H a primary alcohol OOH RCR' RCR' a ketone + H2 Pt H a secondary alcohol 33 Examples: Hydrogenation Reactions • Complete the following reactions: O CH 3 CH 2 O CH 3 O CCH 3 CH H + Pt 2 + PtH 2 + PtH 2 34 .
Chapter 4 Notes Addition of Alcohols to Aldehydes • Aldehydes react with alcohols first to form hemiacetals . which then react with excess alcohol to produce ketals . O RCR' ketone H+ R'' OH OH RCR' OR'' hemiketal ketal H+ R''' OH OR''' RCR' OR'' O CH 3 CCH 3 OCH 3 OH CH 3 CCH OCH 3 3 CH 3 CCH OCH 3 3 36 . OOHOR'' RCH aldehyde H+ R' OH H+ R'' OH RCH OR' hemiacetal acetal RCH OR' OOHOCH CH 3 CH H+ CH 3 OH 3 CH 3 CH OCH 3 H+ CH 3 OH CH 3 CH OCH 3 35 Addition of Alcohols to Ketones • Ketones react with alcohols first to form hemiketals . which then react with excess alcohol to produce acetals .
and Ketals (oh my) OH CH 3 CH OCH 3 a hemiacetal hemiacetal carbon OCH 3 CH 3 CH OCH 3 an acetal acetal carbon OH CH 3 CCH OCH 3 a hemiketal 3 hemiketal carbon OCH 3 CH 3 CCH OCH 3 a ketal 3 ketal carbon 37 Examples: Identifying Acetals and Ketals • Identify the following compounds as being acetals. OH CH 3 OCHCH 3 OCH CH 3 OCH 2 CH 2 OH CH 3 3 3 CH 2 OCCH CH 3 OH CH 3 O OCH 3 OO OCH 3 38 .Chapter 4 Notes Hemiacetals. Hemiketals. or hemiketals. Acetals. hemiacetals. ketals.
ketals. or hemiketals. hemiacetals.Chapter 4 Notes Examples: Identifying Acetals and Ketals • Identify the following compounds as being acetals. CH 3 O CH 3 CH C H + CH 3 OH H+ CH 3 O CH 3 CH C CH 3 + CH 3 CH 2 OH H+ 40 . 3 O OH CH 3 O OCH OOCH 3 CH 2 CH 3 H OH OOCH 3 OCH 2 CH 3 OH CH 2 CH 2 CH 3 CH 2 CH 2 CH 3 39 Examples: Formation of Acetals and Ketals • Complete the following reactions.
producing a cyclic hemiacetal or hemiketal: O H CH H2 C H2 C OH O CH 2 H+ OH C H2 OH O H H H+ OCH 3 O + CH 3 OH + H2 O 41 Intramolecular Addition Reactions • These kinds of reactions are very important in carbohydrate chemistry: O C1 HOH C 2 HOH C 3 HO H C 4 H 6 D- H 6 CH 2 OH HC H + 5 O H C2 OH OH C1 H C4 HO H OH C3 H ß-D glucose C5 OH CH 2 OH glucose 42 . an intramolecular addition reaction can occur.Chapter 4 Notes Intramolecular Addition Reactions • In molecules which have both OH and C=O groups on different carbon atoms.
Chapter 4 Notes Hydrolysis of Acetals and Ketals • Under acidic conditions. OCH 3 CH 3 CH OCH 3 OCH 2 CH 3 CH 3 CCH 2 CH 2 CH 3 H+ + H2 O + H 2O H+ OCH 2 CH 3 O OH + H 2O CH 3 H+ 44 . OR' O RCH OR' acetal H+ + H2O RCH+ 2 R'—OH aldehyde alcohol OR'' O RCR' OR'' ketal + H 2 O + 2 R''—OH H+ RCR' ketone alcohol 43 Examples: Hydrolysis of Acetals and Ketals • Complete the following reactions. • This is an example of a hydrolysis reaction. and regenerate the original aldehyde or ketone from the acetal or ketal. in which water causes a compound to be split into its component substances. water can be used to reverse the previous reaction.
Addition of an Alcohol to an Aldehyde to form an Acetal O OH RC aldehyde HRC H+ ROH H OR hemiacetal acetal H+ ROH RC OR H OR 6. Hydrolysis of a Ketal to give a Ketone OR + O H + H2 O H + RC aldehyde H + 2 ROH alcohol O R + H2 O H RC ketone R + 2 ROH alcohol 46 RC OR ketal . Hydrogenation of Ketones to give Secondary Alcohols O RC RRC H2 + ketone Pt O H R H secondary alcohol 45 5. Oxidation of Aldehydes to give Carboxylic Acids O O [O] RC HRC aldehyde OH carboxylic acid 2.Chapter 4 Notes Reactions of Aldehydes and Ketones 1. Oxidation of Ketones — No Reaction O RC R ketone [O] NR 3. Hydrolysis of an Acetal to give an Aldehyde OR RC OR acetal 8. Addition of an Alcohol to a Ketone to form a Ketal O OH RC ketone RRC H+ ROH R OR hemiketal ketal H+ ROH RC OR R OR 7. Hydrogenation of Aldehydes to give Primary Alcohols O + RC HRC H2 aldehyde Pt O H H H primary alcohol 4.
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