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Organic Chemistry/Ketones and aldehydes
< Organic Chemistry

Aldehydes (
) and ketones (
) are both carbonyl compounds. They are organic
compounds in which the carbonyl carbon is connected to C or H atoms on either side. An aldehyde
has one or both vacancies of the carbonyl carbon satisfied by a H atom, while a ketone has both its
vacancies satisfied by carbon.
Contents
[hide]

1 Naming Aldehydes and Ketones

2 Boiling Points and Bond Angles

3 Preparing Aldehydes and Ketones
o

o

3.1 Preparing Aldehydes

3.1.1 Partial oxidation of primary alcohols to aldehydes

3.1.2 From fatty acids

3.1.3 Stephen reduction

3.1.4 Rosenmund reaction

3.2 Preparing Ketones

3.2.1 From Grignard reagents

3.2.2 From nitriles

3.2.3 From gem dihalides

3.2.4 Oppenaur oxidation

a number designation is not needed.1.4 Hydration of alkynes  4 Keto-enol tautomerism  5 Reactions of Aldehydes and Ketones o 5.1 Nucleophilic addition o 5.5-heptanedione. a hexane ring with a formyl group is named cyclohexanecarbaldehyde.5 Friedel-Crafts acylation of aromatic compounds  3. Alternatively. The above example of 2-butanone can also be named ethyl methyl ketone using this method. gets the lowest number.3.3 Oxidation 6 Inductive Effect and Greek letter assignment Naming Aldehydes and Ketones[edit] Ketones are named by replacing the -e in the alkane name with -one.3 Ozonolysis of alkenes  o 3. functional class nomenclature of ketones is also recognized by IUPAC. For example. the ending -dione would be added to the alkane name. Since an aldehyde is always at the carbon that is numbered one. The -CH=O group of aldehydes is known as a formyl group. When a formyl group is attached to a ring. If two ketone groups are on the same structure. such as 2.2 Reactions with the carbonyl oxygen o 5. Aldehydes replace the -e ending of an alkane with -al for an aldehyde. the aldehyde of pentane would simply be pentanal. ending with the word ketone.1 Mechanism 3. For example. would be named 2-butanone because the root structure is butane and the ketone group is on the number two carbon.6 Oxidation of secondary alcohols to ketones 3. called the carbonyl group. . The carbon chain is numbered so that the ketone carbon.2. For example. which is done by naming the substituents attached to the carbonyl group in alphabetical order.o  3. the ring name is followed by the suffix "carbaldehyde".2.1 Reactions with the carbonyl carbon   5.

From fatty acids[edit] (HCOO)2Ca + HEAT ----> HCHO + CaCO3 (CH3COO)2Ca + HEAT ----> acetone + CaCO3 (CH3COO)2Ca + (HCOO)2Ca ---->ethanaldehyde Stephen reduction[edit] RCN + SnCl2 ----> RCH=NH2+Cl− ----> on hydrolysis gives RCHO Here sulfur is used as a poisoner so that aldehyde formed doesn't get oxidised to the carboxylic acid. yet lower than alcohols. They are more polar than alkenes and ethers. which makes them rather polar molecules. See the Wikipedia article for more detail. Rosenmund reaction[edit] RCOCl + Pd + BaSO4 + S ---->RCHO for solvent xylene is used Preparing Ketones[edit] From Grignard reagents[edit] RCOOR' + R'MgX ---->RCOR + R'OH R' R' OH | | | RC=O + R'-MgX ---->R-C-OMgX----->R-C-OH + Mg-X | | | O-R' OR' OR' From nitriles[edit] RCN + R'MgX ----> RCOR'(after hydrolysis) HCN does not react with RMgX as HCN has acidic hydrogen which results in RH being formed. . Typical bond angles between the carbonyl group and its substituents show minor deviations from the trigonal planar angles of 120 degrees. with a slightly higher bond angle between the O=C-R bond than the R-C-R bond on the carbonyl carbon (with R being any substituent). thus making their relative boiling points higher than alkenes and ethers. Preparing Aldehydes and Ketones[edit] Preparing Aldehydes[edit] Partial oxidation of primary alcohols to aldehydes[edit] This reaction uses pyridinium chlorochromate (PCC) in the absence of water (if water is present the alcohol will be oxidized further to a carboxylic acid).Boiling Points and Bond Angles[edit] Aldehyde and ketone polarity is characterized by the high dipole moments of their carbonyl group. though because they lack hydrogen. they cannot participate in hydrogen bonding like alcohols.

which would otherwise react with the aldehydes and ketones. generally in the presence of a reducing agent.From gem dihalides[edit] RCCl2R + strong base ----> RCOR Oppenaur oxidation[edit] Reagent is Aluminium tert. but is treated directly with water. butoxide solvent is acetone ROH + ACETONE ----> Ketone + isopropyl alcohol this oxidation does not affect double bonds in this oxidation ketone act as a oxidizing agent this is exact opposite to merrwine pondroff reduction Friedel-Crafts acylation of aromatic compounds[edit] An aromatic ring reacts with a carboxylic acid chlorine (RCOCl) in the presence of AlCl 3 to form an aryl ketone of the form ArCOR. This unstable. Cr2O72-. the molozonide reverts to its corresponding carbonyl oxide (also called the Criegee intermediate or Criegee zwitterion) and aldehyde or ketone in a retro-1. are often converted into acids. Ozonolysis (cleavage "by ozone) is carried out in two stages: first. is to prevent formation of hydrogen peroxide. Oxidation of secondary alcohols to ketones[edit] A secondary alcohol can be oxidised into a ketone using acidified potassium dichromate(VI) and heating under reflux. aldehyde or ketone if oxidisable can further oxidise into carboxylic acid which is not the case with reducing agents In the cleavage products a doubly-bonded oxygen is found attached to each of the originally doublybonded carbons. evaporation of the solvent leaves the ozonide as a viscous oil.3-dipolar cycloaddition or produce a relatively stable ozonide intermediate (a trioxolane) . Ozone gas is passed into a solution of the alkene in some inert solvent like carbon tetrachloride. is reduced to the green Cr3+(aq) ion. explosive compound is not purified. Ozonolysis of alkenes[edit] It is a reaction in which the double bond is completely broken and the alkene molecule converted into two smaller molecules. hydrolysis of the ozonide to yield the cleavage products. If oxidsing reagent is used. RCOOH. The orange dichromate(VI) ion. and second.) Mechanism[edit] The alkene and ozone form an intermediate molozonide in a 1. (Aldehydes. RCHO. The function of the reducing agent. The oxide and aldehyde or ketone react again in a 1. which is frequently zinc dust.3-dipolar cycloaddition.3-dipolar cycloaddition. addition of ozone to the double bond to form an ozonide . Next. for ease of isolation.

Hydration of alkynes[edit] Water is added to an alkyne in a strong acid. They are known as tautomers of each other. and a hydrogen from water will be abstracted by the carbonyl oxygen. The presence of α-hydrogen is necessary for this equilibrium: those compounds not possessing it are called non-enolizable ketones. protonation of the oxygen group will occur. In the presence of a base. deprotonation of the alpha hydrogen will occur.e. and water will abstract an alpha (α) hydrogen. Keto-enol tautomerism[edit] In the presence of an acid (H+) or a base (OH-). In the presence of an acid. the equilibrium of carbonyl compounds between two forms. in which the double bond of the carbonyl group migrates to form double bond between the carbonyl and the alpha (α) carbon. not isomers. the aldehyde or ketone will form an equilibrium with enols. The strong acid used is sulfuric acid and mercuric acid. It must be stressed that the keto and the enol forms are two distinct compounds. This is an important feature of ketone and aldehydes. and is known as the keto-enolic tautomery or keto-enol tautomerism. i. .

when aldehydes react with fehling solution a red precipitate is obtained (due to formation of Cu2O) . Alpha (α) carbons are directly attached to the carbonyl group. adjacent carbons are named using Greek letters in order of closeness to the carbonyl group. the partially positive carbon atom can act as an electrophile. Nucleophilic addition[edit] With cyanide.+ H+ → RR'COHCN e. nucleophilic addition occur to give a hydroxynitrile: RR'C=O + CN.Mechanism of enol-keto tautomerism Reactions of Aldehydes and Ketones[edit] Reactions with the carbonyl carbon[edit] Since aldehydes and ketones contain a polar carbonyl group. the alpha (α) hydrogens are especially acidic. aldehydes but not ketones may be oxidized into carboxylic acids. meaning they are especially prone to removal. gamma (γ) to beta (β). beta (β) carbons are connected to alpha carbons. and so on. Benedict's/Fehling's reagent (essentially alkaline Cu +2). . but a ketone will not react. or be attacked by electrophiles. as well as the stabilizing resonance of the double bond between the hydroxyl group and conjugated carbons to the carbonyl group. and adjacent carbons are effected by induction. resulting in a net addition to the molecule. Due to the inductive effect of the partial positive charge on the carbonyl carbon of a keytone or aldehyde. This is one way to test for the presence of an aldehyde in a sample compound: an aldehyde will become a carboxylic acid when reacted with Tollens' reagent. Oxidation[edit] Using a strong oxidizing agent such as the Tollens' Reagent (Ag2O in aqueous ammonia) acidified dichromate. Using the carbonyl group as a reference. Strong and weak nucleophiles are able to attack this carbonyl carbon. propanone → 2-hydroxymethylpropanonitrile Reactions with the carbonyl oxygen[edit] The partially negative oxygen can act as a nucleophile.g. Inductive Effect and Greek letter assignment[edit] The carbonyl group is very electron withdrawing.