CHEM 2301 Chapter Notes - Chapter 9: Organic Compound, Weak Base, Nucleophilic Substitution

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2 Apr 2017

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Document Summary

Functional groups that contain polar co sigma bonds. Alcohols contain a hydroxy group oh bonded to an sp2 hybridized c. Classified as primary, secondary or tertiary based on the number of c atoms bonded to the c with the oh. Ethers have 2 alkyl groups bonded to an o atoms. Is symmetrical id the groups are the same or unsymmetrical if they are different. Alcohols and ethers are organic derivatives of water formed by replacing a h on the o by and r group. Epoxides are ethers having the o atom in a 3 membered ring. These all contain an o atom surrounded by 2 atoms and 2 nonbonded electron pairs making hte o tetrahedral and sp3 hybridized. Alcohols and ethers have a bent shape like water. Bond angle is similar to water as 109. 5 degrees. Have angle strain making them much more reactive.

Related Questions

Â¥Write a brief (less than 150 words, 3 or 4 sentences) of the aim of the experiment

Â¥Address question of what was done, how it was done, and what compounds were used.

Â¥Include Chemical Reaction where relevant.

See text below. Please provide Purpose following the steps above. Thank you.

Alcohols R-O-H are characterized by the presence of the hydroxyl group

Because of intermolecular co-association, alcohols show higher boiling points

than aldehydes, ethers, or ketones of similar mass. Among alcohols, boiling

points increase with increased surface area. Increased surface area occurs as

more carbons are added to the alkyl portion or with decreased branching of th

alkyl group. Thus, 1-propanol has a higher boiling point than ethanol

(increased C#). 1-propanol also has a higher boiling point than 2-propanol

(decreased branching)

The solubility of alcohols in water decreases as the surface area of the

alkyl (nonpolar) portion increases. Thus, alcohols become less soluble in water

as the number of carbons in the alkyl group increases. When comparing

alcohols that contain the same number of carbons, branching of the alkyl group

decreases its surface area and thus increases the water solubility of the alcohol.

1-Propanol is slightly soluble in water while 2-propanol is quite soluble

The limit of water solubility is reached at about 4 or 5 carbons in the

alkyl group. However, it is possible to "salt out" or separate a water-soluble

alcohol from the water it is mixed with by the addition of certain salts such as

K2CO3. If an alcohol-water mixture is saturated with such a salt, the anion

selectively forms strong ion-dipole bonds to water, leaving the alcohol as a

separate layer. Thus, water is separated from the alcohol because the ionic salt

bonds more strongly with water than with the alcohol. There are twice as many

ion-dipole bonds possible with water than with the alcohol.

Alcohols are relatively acidic organic molecules, being weaker acids than

water, yet stronger than acetylene.

Acidity: water > alcohol > acetylene > ammonia > alkanes

Alcohols may be converted to sodium alkoxides by the action of metallic sodium

under anhydrous conditions. Primary alcohols react more readily tharn

secondary or tertiary alcohols due to the relative stability of the alkoxide ions in

the solvent alcohol.

R-o:-

Alcohols undergo nucleophilic substitution reactions with ease under

acidic conditions. The relative ease of such substitution for primary, secondary

and tertiary alcohols serves as a means of classification. Upon treatment with

concentrated HC1, tertiary alcohols are rapidly converted to alkyl chlorides

Secondary alcohols require warming in a boiling water bath for 15 minutes

Primary alcohols do not react at all under these conditions. The alkyl chlorides

formed by this reaction are insoluble in the concentrated HCl and form an

easily detectable second layer

R-O-H HC1 >

Ð-Ð-Ð

Complications arise from the fact that benzylic and allylic alcohols also

react immediately, but yield products that are soluble in the concentrated HCI

Alcohols are easily oxidized by any of these strong oxidizing agents:

dilute KMnO4, NajCr.07 in acid, or CrO3 (chromic anhydride)

acidified sodium dichromate is somewhat helpful in the classification of

alcohols. Prim

ary and secondary alcohols are oxidized rapidly within several

minutes, while tertiary alcohols do not react under these conditions

Oxidation occurs more easily when the carbon bearing the -OH group

bonded to at least one atom of hydrogen. The complex mechanism of

involves the transfer of a hydride ion H:- as a critical step.

hydrogen atom is absent (as in tertiary alcohols), no oxidation can occur

directly. Tertiary alcohols may be oxidized indirectly through the formation of

Alcohols which contain the partial structure C- CH3 give positive

Ð¾Ð½

results in the iodofora reaction. When the alcohol is dissolved in water and

KOH, the addition of a solution of 12 in KI yields a yellow precipitate of

iodoform, CHI3, along with the oxidized portion of the alcohol

Hypoiodite ion is produced by the reaction between molecular iodine and

hydroxide ion:

I2 + 4(OH) -

The hypoiodite ion in turn oxidizes an alcohol with the proper structure

Once this oxidation has occurred, additional hypoiodite ion continues to

react with the aldehyde or ketone produced:

CH,-C

3 (0I)-IC-c3 (OH)-

resulting in the final substitution reaction to give iodoform and the anion of a

carboxylic acid containing one carbon atom less than the original alcohol:

128

lodoform precipitates as fine yellow crystals. This precipitate, a result of a

specific oxidation followed by a substitution, is an indication of the partial

structure of the original alcohol.

Simple alcohols of up to ten carbon atoms may be detected by the

ammonium hexanitrocerrata(lV) reagent, (NH4Ce(NO,). The hexanitro-

cerrate(IV) ion has a distinctive orange-red color. When an alcohol, ROH is

added, one or more OR- groups replace the nitro groups as ligands in the

complex ion. The new complex ion formed has a distinctive color. The general

equation for this reaction is:

This test is positive for aliphatic alcohols up to approximately ten carbons in

length. Phenols or larger alcohols yield insoluble mixtures

Alcohols react with acids or with acid derivatives to form esters. This

characteristic reaction is useful in the formation of specific esters such as ethyl

acetate, acetylsalicylic acid (aspirin) and methyl salicylate (oil of wintergreen). In

this experiment, methyl salicylate will be prepared by reacting methyl alcohol

with salicylic acid in the presence of a trace of sulfuric acid as the catalyst

Lower molecular weight alcohols such as ethanol, methanol, and

isopropyi alcohol absorb water on exposure to moist air or are prepared as

azeotropic mixtures containing water. The presence of water in alcohols may be

detected in several ways. If a small lump of CaC2 is added to any alcohol that

contains a trace of water, a reaction occurs that produces immediate bubbles of

acetylene gas:

Thus, evolution of acetylene gas upon the addition of calcium carbide indicates

the presence of water in the alcohol. Another way to test for the presence of

water in alcohols involves the use of anhydrous cupric sulfate powder (CuSO4)

Anhydrous cupric sulfate is a very pale, almost white powder. In the presence of

water, deep blue crystals of cupric sulfate pentahydrate,

CuSO4-5H20, are formed. Thus, anhydrous cupric sulfate indicates the

presence of water in an alcohol by a simple color change.

Commercial ethanol is produced as an azeotropic mixture that contains

95% ethanol and 5% water. Absolute alcohol contains no water. Many reagent

grade alcohols are composed of a nonpotable mixture of 95% ethanol and 5%

isopropyl alcohol. Thus, absolute ethanol and reagent alcohols are both water

free and give negative results when tested for the presence of water

Classify each of the following statements as true or false:

a) To be classified as organic, a compound must be or have been part of a living organism.

b) Carbon atoms normally form four bonds in organic compounds.

c) Only an unsaturated hydrocarbon can engage in an addition reaction.

d) Members of a homologous series differ by a distinct structural unit.

e) Alkanes, alkenes, and alkynes are unsaturated hydrocarbons.

f) Alkyl groups are a class of organic compounds.

g) Isomers have the same molecular formulas but different structural formulas.

h) Cis-trans isomerism appear among alkenes but not alkynes.

i) All aliphatic hydrocarbons are unsaturated.

j) Aromatic hydrocarbons have a ring structure.

k) An alcohol has an alkyl group bonded to an oxygen atom, and an ether has two.

l) Carbonyl groups are found in alcohols and aldehydes.

m) An ester is an aromatic carbon made from the reaction of an alcohol and a carboxylic acid.

n) An amine has one, two, or three alkyl groups substituted for hydrogens in an ammonia molecule.

o) An amide has the structure of a carboxylic acid except that replaces OH in the carboxyl group.

p) A peptide linkage series arises when a water molecule forms from a hydrogen from the of one amino acid molecule an from an another amino acid molecule.