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ALCOHOL, ETHER & AMINES

Definition of alcohol
An alcohol is any organic compound in which a hydroxyl functional group (-OH) is bound to a carbon atom, usually connected to other carbon or hydrogen atoms

Definition of ether
Ethers ( /ir/) are a class of organic compounds that contain an ether group an oxygen atom connected to two alkyl or aryl groups of general formula ROR'. A typical example is the solvent and anesthetic diethyl ether, commonly referred to simply as "ether" (CH3-CH2-O-CH2-CH3)

Definition of amines
Amines are organic compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are derivatives of ammonia, where in one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group

Physical and Chemical Properties of Alcohol

Have an odor that often described as 'biting' and as 'hanging' in nasal passages. Protic solvents
The hydroxyl group makes the alcohol molecule polar. Those groups can form hydrogen bonds to one another and to other compounds (except in certain large molecules where the hydroxyl is protected by steric hindrance of adjacent groups.

Two opposing solubility trends in alcohols


The tendency of the polar OH to promote solubility in water The tendency of the carbon chain to resist it

All simple alcohols are miscible in organic solvents

Have higher boiling points than comparable gydrocarbon and ethers because of hydrogen bonding
The boiling point of the alcohol ethanol is 78.29 C, compared to 69 C for the hydrocarbon Hexane (a common constituent of gasoline), and 34.6 C for Diethyl ether

Can show either acidic or basic properties at the O-H group


Slightly weaker acids than water but still able to react with strong bases such as Sodium Hydride or reactive metals such as Sodium Salts that results are called alkoxides, with the general formula RO- M+

The oxygen atom has lone pairs of nonbonded electrons that render it weakly basic in the presence of strong acids such as sulfuric acids
Eg: Methanol

Preparation of Alcohol

Substitution

Primary alkyl halides react with aqueous NaOH or KOH mainly to primary alcohols in nucleophilic aliphatic substitution. (Secondary and especially tertiary alkyl halides will give the elimination (alkene) product instead). Grignard reagents react with carbonyl groups to secondary and tertiary alcohols. Related reactions are the Barbier reaction and the Nozaki-Hiyama reaction.

Reduction

Aldehydes or ketones are reduced with sodium borohydride or lithium aluminium hydride (after an acidic workup). Another reduction by aluminiumisopropylates is the Meerwein-Ponndorf-Verley reduction. Noyori asymmetric hydrogenation is the asymmetric reduction of -keto-esters.

Hydrolysis

Alkenes engage in an acid catalysed hydration reaction using concentrated sulfuric acid as a catalyst that gives usually secondary or tertiary alcohols. The hydroboration-oxidation and oxymercurationreduction of alkenes are more reliable in organic synthesis. Alkenes react with NBS and water in halohydrin formation reaction. Amines can be converted to diazonium salts, which are then hydrolyzed.

Application of alcohols

Ethylene glycol Alcohol fuel (mainly ethanol and methanol) Reagents or solvents

As an antifreeze

Because of low toxicity and ability to dissolve non-polar substances Ethanol is used as a solvent in medical drugs, perfumes, and vegetable essencess such as vanilla Organic synthesis - serve as versatile intermediates

Application of alcohols

Antiseptic

Disinfect the skin before injections are given, often along with iodine Not require drying due to volatility of the compound

Ethanol-based soaps Preservative for speciments

Alcohol gels

hand sanitizers

Physical properties of Ether

Ether molecules cannot form hydrogen bonds with each other


relatively low boiling points compared to the analogous alcohols

In the boiling points of the ethers and their isometric alcohols becomes lower as the carbon chains become longer
Because the van der Waals interactions of the extended carbon chain dominates over the presence of hydrogen bonding

Slightly polar
The C-O-C bond angle in the functional group is about 110, and the C-O dipoles do not cancel out

Ethers are more polar than alkenes but not as polar as alcohols, esters, or amides of comparable structure
However, the presence of two lone pairs of electrons on the oxygen atoms makes hydrogen bonding with water molecules possible

Cyclic ethers such as tetrahydrofuran and 1,4-dioxane are miscible in water


Because of the more exposed oxygen atom for hydrogen bonding as compared to aliphatic ethers

Reactions of Ether

Ether cleavage

Although ethers resist hydrolysis, they are cleaved by mineral acids such as hydrobromic acid and hydroiodic acid. Hydrogen chloride cleaves ethers only slowly Methyl ethers typically afford methyl halides: ROCH3 + HBr CH3Br + ROH These reactions proceed via onium intermediates, i.e. [RO(H)CH3]+Br Some ethers rapidly cleave with boron tribromide (even aluminium chloride is used in some cases) to give the alkyl bromide Depending on the substituents, some ethers can be cleaved with a variety of reagents, e.g. strong base.

Peroxide formation

When stored in the presence of air or oxygen, ethers tend to form explosive peroxides, such as diethyl ether peroxide The reaction is accelerated by light, metal catalysts, and aldehydes In addition to avoiding storage conditions likely to form peroxides, it is recommended, when an ether is used as a solvent, not to distill it to dryness, as any peroxides that may have formed, being less volatile than the original ether, will become concentrated in the last few drops of liquid.

Lewis bases

Ethers serve as Lewis bases and Bronsted bases Strong acids protonate the oxygen to give "onium ions." For instance, diethyl ether forms a complex with boron trifluoride, i.e. diethyl etherate (BF3.OEt2) Ethers also coordinate to Mg(II) center in Grignard reagents Polyethers, including many antibiotics, cryptands, and crown ethers, bind alkali metal cations strongly.

Alphahalogenation

This reactivity is akin to the tendency of ethers with alpha hydrogen atoms to form peroxides Chlorine gives alpha-chloroethers.

Preparation of Ether

Dehydration of alcohols

The Dehydration of alcohols affords ethers: 2 R-OH R-O-R + H2O at high temperature This direct reaction requires elevated temperatures (about 125 C) The reaction is catalyzed by acids, usually sulfuric acid The method is effective for generating symmetrical ethers, but not unsymmetrical ethers Diethyl ether is produced from ethanol by this method Cyclic ethers are readily generated by this approach. Such reactions must compete with dehydration of the alcohol: R-CH2-CH2(OH) R-CH=CH2 + H2O The dehydration route often requires conditions incompatible with delicate molecules Nucleophilic displacement of alkyl halides by alkoxides : R-ONa + R'-X R-O-R' + NaX This reaction is called the Williamson ether synthesis. It involves treatment of a parent alcohol with a strong base to form the alkoxide, followed by addition of an appropriate aliphatic compound bearing a suitable leaving group (R-X) Suitable leaving groups (X) include iodide, bromide, or sulfonates This method usually does not work well for aryl halides (e.g. bromobenzene (see Ullmann condensation below) Likewise, this method only gives the best yields for primary halides. Secondary and tertiary halides are prone to undergo E2 elimination on exposure to the basic alkoxide anion used in the reaction due to steric hindrance from the large alkyl groups. In a related reaction, alkyl halides undergo nucleophilic displacement by phenoxides The R-X cannot be used to react with the alcohol However, phenols can be used to replace the alcohol, while maintaining the alkyl halide. Since phenols are acidic, they readily react with a strong base like sodium hydroxide to form phenoxide ions The phenoxide ion will then substitute the -X group in the alkyl halide, forming an ether with an aryl group attached to it in a reaction with an SN2 mechanism : C6H5OH + OH- C6H5-O- + H2O : C6H5-O- + R-X C6H5OR The Ullmann condensation is similar to the Williamson method except that the substrate is an aryl halide Such reactions generally require a catalyst, such as copper. Alcohols add to electrophilically activated alkenes : R2C=CR2 + R-OH R2CH-C(O-R)-R2 Acid catalysis is required for this reaction. Often, mercury trifluoroacetate (Hg(OCOCF3)2) is used as a catalyst for the reaction, geneating an ether with Markovnikov regiochemistry Using similar reactions, tetrahydropyranyl ethers are used as protective groups for alcohols.

Williamson ether synthesis

Ullmann condensation

Electrophilic addition of alcohols to alkenes

Preparation of epoxides

Epoxides are typically prepared by oxidation of alkenes The most important epoxide in terms of industrial scale is ethylene oxide, which is produced by oxidation of ethylene with oxygen Other epoxides are produced by one of two routes: By the oxidation of alkenes with a peroxyacid such as m-CPBA. By the base intramolecular nucleophilic substitution of a halohydrin.

Classes of amines

Aliphatic amines
Primary alkyl amines include methylamine, ethanolamine (2-aminoethanol), and the buffering agent tris

Aromatic amines
Aromatic amines have the nitrogen atom connected to an aromatic ring as in anilines

Secondary amines have two alkyl substituents bound to N together with one hydrogen. Important representatives include dimethylamine and methy lethanolamine

The aromatic ring decreases the alkalinity of the amine, depending on its substituents

In tertiary amines, all three hydrogen atoms are replaced by organic substituents

The presence of an amine group strongly increases the reactivity of the aromatic ring, due to an electron-donating effect.

Physical properties of Amines

The boiling point of amines is higher than those of the corresponding phosphines, but generally lower than those of the corresponding alcohols

Methylamine and ethylamine are gases under standard conditions

Methyl alcohol and ethyl alcohols are liquid in standard conditions

Physical properties of Amines

Most aliphatic amines display some solubility in water

Solubility decreases with the increase in the number of carbon atoms

Aliphatic amines display significant solubility in organic solvents, especially polar organic solvents

Primary amines react with Ketones such as acetones

Application of amines

Dyes

Application of amines

Drugs

Gas treatment

Dyes

Primary aromatic amines are used as a starting material for the manufacture of azo dyes. It reacts with nitric(III) acid to form diazonium salt, which can undergo coupling reaction to form azo compound. As azo-compounds are highly coloured, they are widely used in dyeing industries

Methyl orange

Direct Brown 138

Sunset Yellow

Ponceau

Drugs

Chlorpheniramine

An antihistamine that helps to relieve allergic disorders due to cold, hay fever, itchy skin, insect bites and stings.

Chlorpromazine

A tranquillizer that sedates without inducing sleep. It is used to relieve anxiety, excitement, restlessness or even mental disorder.

Ephedrine and Phenylephrine

, as amine hydrochlorides, are used as decongestants.

Amphetamine, Methamphetamine, and Methcathinone

are psychostimulant amines that are listed as controlled substances by the US DEA.

Amitriptyline, Imipramine, Lofepramine and Clomipramine

are tricyclic antidepressants and tertiary amines.

Nortriptyline, Desipramine, and Amoxapine

are tricyclic antidepressants and secondary amines. (The tricyclics are grouped by the nature of the final amine group on the side chain.)

Gas treatment

- Aqueous monoethanolamine (MEA) - diglycolamine (DGA) - diethanolamine (DEA) - diisopropanolamine (DIPA) - methyldiethanolamine (MDEA)

- removing carbon dioxide(CO2) and hydrogen sulfide (H2S) from natural gas - refinery process streams - remove CO2 from combustion gases / flue gases - may have potential for abatement ofgreenhouse gases