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Ch. 4: Alcohols and Alkyl Halides OHC XC

alcohol alkyl halide (X= F, Cl, Br, I)

4.1: Functional Groups - >11 million organic compounds which are classified into families according to structure and reactivity.

Functional Group (FG): a group of atoms, which are part of a larger molecule, that have characteristic chemical behavior. FG’s behave similarly in every molecule they are part of.

The chemistry of organic molecules is defined by the function groups it contains

H3C

HO

HH

H3CH

C CH

HH

H

H3C

HO

HH

H3CH

C CBr

HH

BrH H

Br Br

Br2

Br2

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C C

C C

C CC

CCC

H H

H

HH

Alkenes

Alkynes

Arenes

C C

Alkanes

Carbon - Carbon Multiple Bonds

C NO

nitro alkaneOC X

X= F, Cl, Br, IAlkyl Halide

Carbon-heteroatom single bonds

C O C CO

alcohols ethers

H

C N

amines

C SH C CS

thiols sulfides (thioethers)

acidic

basic

C CO

epoxide

C CSS

disulfide

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C H

O

C C

O

Carbonyl-oxygen double bonds (carbonyls)

aldehyde

ketones

C O

OH

C O

OC

carboxylic acid

ester

C Cl

O

acid chloride

C O

O

C

O

anhydrides

C N

O

amide

acidicCarbon-nitrogen multiple bonds

N

imine(Schiff base)

C C N

basic

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4.2: IUPAC Nomenclature of Alkyl Halides (please read) Use the systematic nomenclature of alkanes; treat the halogen as

a substituent of the alkane.

F- fluoro, Cl- chloro, Br- bromo, I- iodo

4.3: IUPAC Nomenclature of Alcohols 1.  In general, alcohols are named in the same manner as

alkanes; replace the -ane suffix for alkanes with an -ol for alcohols

2.  Number the carbon chain so that the hydroxyl group gets the lowest number

3.  Number the substituents and write the name listing the

substituents in alphabetical order.

CH3CH2CH2CH3 CH3CH2CH2CH2OHOH

butane 1-butanol 2-butanol

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4.4: Classes of Alcohols and Alkyl Halides - Alcohols and alkyl halides are classified as according to the degree of substitution of the carbon bearing the halogen or -OH group

primary (1°) : one alkyl substituent secondary (2°) : two alkyl substituents tertiary (3°) : three alkyl substituents

Many alcohols are named using non-systematic nomenclature OH OH OHC

H3C

H3CH3C

benzyl alcohol(phenylmethanol)

allyl alcohol(2-propen-1-ol)

tert-butyl alcohol(2-methyl-2-propanol)

HOOH

ethylene glycol(1,2-ethanediol)

glycerol(1,2,3-propanetriol)

OHHOOH

OCH

HH H

OCR

HH HOC

R

HR HOC

R

RR H

1° carbon 2° carbon 3° carbon

methanol primary secondary tertiary

OH

2-methyl-2-pentanol

OH

3-phenyl-2-butanol

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4.5: Bonding in Alcohols and Alkyl Halides - the C-X bond of alkyl halides and C-OH bond of alcohols has a significant dipole moment.

HC O

HH

δ+Hδ+

δ-HC Cl

HH

δ+ δ-

µ = 1.9 µ = 1.7

4.6: Physical Properties of Alcohols and Alkyl Halides: Intermolecular Forces

H2O CH3CH2CH2CH3 CH3CH2CH2CH2Cl CH3CH2CH2CH2OH MW=18 MW=58 MW=92.5 MW=74 bp= 100° C bp= -0° C bp= 77° C bp= 116° C

CH3CH2Cl CH3CH2OH MW= 64.5 MW=60 bp= 12° C bp= 78° C

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Like water, alcohols can form hydrogen bonds: a non-covalent interaction between a hydrogen atom (δ+) involved in a polar covalent bond, with the lone pair of a heteroatom (usually O or N), which is also involved in a polar covalent bond (δ-)

O H

O Hδ- δ+

N H

N Hδ- δ+

C O C O

C Oδ-δ+

H HO

H

HO

H

HO

H

HO

H

HOH

HO

H

HO

H HO

H

HOH

HO

H

HO

H

HO

R

H OH

RO

R

H OH

RO

R

H O

RO

H

δ

δδ

δ

δ

δδ

δ

δ

δ

δ

δ

Hydrogen-bonds are broken when the alcohol reaches its bp, which requires additional energy

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4.7: Preparation of Alkyl Halides from Alcohols and Hydrogen Halides

R-OH + H-X R-X + HOH

Reactivity of the alcohol:

Reactivity of the H-X : parallels the acidity of HX HF < HCl < HBr < HI

CH

HR C

R

HR C

R

RROH OH OHC

H

HH OH << < <

increasing reactivity

Primary (1°) Secondary (2°) Tertiary (3°)Methyl

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Curved Arrow Convention

1.  Curved arrows show the movement (flow) of electron during bond breaking and/or bond making processes. The foot of the arrow indicates where the electron or electron pair originates, the head of the arrow shows where the electron or electron pair ends up. .

A. The movement of a single electron is denoted by a curved single headed arrow (fishhook or hook).

B. The movement of an electron pair is denoted by a curved double headed arrow.

2. If an electron pair moves in on a new atom, another electron pair must leave so that the atom does not exceed a full valance of eight electrons. There are two common exceptions:

A. When an atom already has an incomplete valance (R3C+). B. With second row (or below) elements the octet rule may be violated.

3. The arrows completely dictate the Lewis structure of the product.

double-headed arrow single-headed

arrow

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Curved Arrow Convention

Other Suggestions for Proper Arrow Pushing: 4.  The natural polarization of double bonds between unlike atoms is in the direction

of the more electronegative atom and this will be the important direction of electron movement.

5. In drawing a mechanism, the formal charges of atoms in the reactants may change in the product. Use your knowledge of Lewis structures and formal charge to determine this.

6. The first step in writing a mechanism is to identify the nucleophile (Lewis base) and the electrophile (Lewis acid). The first arrow is always from the nucleophile to the electrophile.

(CH3)3COH + HCl

The generally accepted mechanism for the reaction of t-butyl alcohol and HCl involves to give t-butyl chloride has three basic steps:

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Mechanism: (CH3)3COH + HCl (CH3)3CCl + H2O

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4.9: Potential Energy Diagrams for Multistep Reactions: The SN1 Mechanism

The rate of oxonium ion formation is very fast The rate of carbocation formation (dissociation of the oxonium ion) is slow The rate of reaction between the carbo- cation and for X- is fast

The overall rate is dependent of the slowest step (rate limiting step)

rate = k [oxonium ion] , where k is the rate constant

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4.10: Structure, Bonding, and Stability of Carbocations - Carbocations are sp2 hybridized and have a trigonal planar geometry

Substituents stabilize a carbocation through: a. Inductive Effects: shifting of electrons in a σ-bond in response to the electronegativity of a nearby atom (or group).

Carbon is a good electron donor. Substitution can also stabilize carbocations by donating electron density through the σ -bond.

3°: three alkyl groups donating electrons

2°: two alkyl groups donating electrons

1°: one alkyl group donating electrons

H HC

H

+H H

C

R

+R H

C

R

+R R

C

R

+

methyl: no alkyl groups donating electrons

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b. Hyperconjugation: The C-H σ-bond on the neighboring carbon lines up with the vacant p-orbital and can donate electron density to the carbon cation. This is a “bonding” interaction and is stabilizing. More substituted carbocations have more possible hyperconjugation interactions.

vacant p-orbital

4.11: Effect of Alcohol Structure on Reaction Rate. The order of reactivity for the reaction:

R3C-OH + H-X R3C-X + HOH where 3° alcohols are most reactive and 1° alcohols are least reactive, reflects the stability of the intermediate carbocation.

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The rate of a reaction is dependent of the activation energy (Eact) There is no formal relationship between ΔGact and ΔG° What is the structure of a transition state? How can the structures of the reactants and products affect ΔGact

The Hammond Postulate provides an intuitive relationship Between rate (ΔGact) and product stability (ΔG°).

Typical reaction coordinate less common

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The Hammond Postulate: The structure of the transition state more closely resembles the nearest stable species (i.e., the reactant, intermediate or product)

For an endothermic reaction (ΔG° > 0), the TS is nearer to the product. The structure of the TS more closely resembles that of the product. Therefore, factors that stabilize the product will also stabilize the TS leading to that product.

For an exothermic reaction (ΔG° < 0), the TS is nearer to the reactant. The structure of the TS more closely resembles that of the reactants.

ΔG°= 0 ΔG°> 0 ΔG°< 0

TS is halfway between reactant and products on the reaction coordinate

TS lies closer to the products than the reactants on the reaction coordinate

TS lies closer to the reactants than the products on the reaction coordinate

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Fig. 4.16

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4.12: Reaction of Primary Alcohols with Hydrogen Halides. The SN2 Mechanism:

Methyl and primary carbocations are the least stable, and they are not likely to be intermediates in reaction mechanism

RH2C-OH + H-X RH2C-X + HOH

SN2 (substitution-nucleophilic-bimolecular).

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4.13: Other Methods for Converting Alcohols to Alkyl Halides Preparation of alkyl chlorides by the treatment of alcohols with thionyl chloride (SOCl2)

R-OH + SOCl2 + base R-Cl + SO2 + HCl

Preparation of alkyl bromides by the treatment of alcohols with phosphorous tribromide (PBr3)

R-OH + PBr3 R-Br + P(OH)3

These methods work best on primary and secondary alcohols. They do not work at all for tertiary alcohols

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4.14: Halogenation of Alkanes

R-H + X2 R-X + H-X

Reactivity: F2 >> Cl2 > Br2 >> I2 4.15: Chlorination of Methane

Mechanism of free radical halogenation has three distinct steps 1. Initiation 2. Propagation 3. Termination

Free radical chlorination is not very useful for making alkyl chlorides: polychlorination, non-specific chlorination

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4.16: Structure and Stability of Free Radicals Free radical: species that contain unpaired electrons

O O N O Cl

Organic (alkyl) radicals are usually highly reactive. The stability and structure of alkyl radicals parallels those of

carbocations: HCH

HHCH

RRCH

RRCR

R< < <

methyl < primary (1°) < secondary (2°) < tertiary (3°)

Radicals are also stabilized by hyperconjugation

Increasing stability

HCH

HHCH

RRCH

RRCR

RH H H H

ΔH° (KJ/mol)= 435 410 397 380

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4.17: Mechanism of Chlorination of Methane Free-radical chain mechanism:

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4.18: Halogenation of Higher Alkanes – free radical chlorination of more substituted carbons is favored, reflecting the stability of the intermediate radical.

CCH

HCH

HCH

HH

H

HH CC

H

HCH

HCH

HH

H

HCl CC

H

ClCH

HCH

HH

H

HH+

(28 %) (72 %)

Cl2, hν

HCH

HCH

C

CH

HH

HH

H

ClCH

HCH

C

CH

HH

HH

H

HCH

HCCl

C

CH

HH

HH

H+

(63 %) (37 %)

four 2° hydrogenssix 1° hydrogens

one 3° hydrogensnine 1° hydrogens

Cl2, hν

HCH

HR

Primary (1°)hydrogens

1.0

HCR

HR

Secondary (2°)hydrogens

3.9

HCR

RR

Tertiary (3°)hydrogens

5.2

< <

Relative rates of free radical chlorination

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Free radical bromination is highly selective

HCH

HR

Primary (1°)hydrogens

1.0

HCR

HR

Secondary (2°)hydrogens

82

HCR

RR

Tertiary (3°)hydrogens

1600

< <

HCH

HCH

C

CH

HH

HH

H

BrCH

HCH

C

CH

HH

HH

H

HCH

HCBr

C

CH

HH

HH

H+

Br2, hν

1 : 99

The propagation step for free radical bromination is endothermic, Whereas chlorination which is exothermic. According to the Hammond postulate the transition state for bromination should resemble the product radical, and therefore be more selective for the product going through the more stable radical intermediate