CHAPTER 4

ALKANE

LECTURER : PHAN THỊ HOÀNG ANH 1

IUPAC nomenclature
International Union of Pure and Applied Chemistry

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The name of every organic molecule has three parts.

• The parent name indicates the number of carbons in the longest continuous
carbon chain in the molecule, which contain the main functional group.
• The suffix indicates what functional group is present.
• The prefix reveals the identity, location, and number of substituents attached
to the carbon chain.
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1. Determine parent chain: longest continuous carbon chain containing the
main functional group

If there are two chains of equal length, pick the chain with more substituents.

NOT

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 2. Number the parent chain: in the direction that give the first substituent the
lower number.

If the first substituents is the same distance from both ends, number the chain to give the
NEXT substituent the lower number.

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When numbering a carbon chain results in the same numbers from either end
of the chain, assign the lower number alphabetically to the first substituent

Note: The prefixes di, tri, tetra, sec, and tert are ignored in alphabetizing
substituent groups, but the prefixes iso, neo, and cyclo are not ignored

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3. Combine substituent names and prefix + parent + suffix.
Use hyphens to separate the different prefixes, and use commas to separate numbers.
If two or more different substituents are present, cite them in alphabetical order.
If two or more identical substituents are present on the parent chain, use one of the
multiplier prefixes di-, tri-, tetra-, and so forth, but don’t use these prefixes for
alphabetizing.

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4. Name a complex substituent as though it were itself a compound.

Number the branched substituent beginning at its point of its attachment to

the main chain

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The common names of these simple alkyl groups are so well entrenched in the
chemical literature that IUPAC rules make allowance for them.

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B. pr. 61.p109 Give the systematic name for each of the following compounds:

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3.

4.

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ALKANE SOURCES
Natural Gas : 75% methane, 10% ethane, and 15% propane, depending on the
source of the gas
Pectroleum: liquid mixture containing hundreds of substances, including
approximately 150 hydrocarbons, roughly half of which are alkanes or
cycloalkanes

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Distillation of crude oil gives a number
of fractions

• Natural gas: C1-C4 – can be

liquefied under pressure
• Gasoline: C5-C11
• Kerosene, jet fuel: C9-C16
• Heating oil, diesel oil: C15-C25
• Lubricants, greasese: highest boiling
fraction
• Asphalt, tar: nonvolatile residue

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ALKANE SYNTHESIS
1) Hydrogenation of alkenes, alkynes

2) Reduction of aldehydes, ketones

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3) Wurtz reaction

R-X + 2Na + X-R ----> R-R + 2NaX

Limited to the synthesis of symmetric alkanes from RI, RBr
Wurtz reaction between two different alkyl halide produce mixture of alkane,
that is, often, difficult to separate
Less effective with tertiary alkyl haldes → elimination reaction produce
alkene

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4) Alkane synthesis using Lithium dialkylcuprate reagents

The lithium dialkylcuprate (also called a Gilman reagent) is formed by the reaction of two
equivalents of the corresponding organolithium reagent with cuprous iodide, cuprous
bromide (CuI, CuBr)

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Steric hindrance makes organocuprates that bear secondary and tertiary alkyl groups less
reactive, and they tend to decompose before they react with the alkyl halide (M)

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The alkyl cross-coupling reaction with Gilman reagents may also be carried out
with aryl, vinyl, allyl, and benzyl halides (L)

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REACTIVITY OF ALKANES
• Alkanes have only strong s bonds
• Electronegativity of C & H are approximately the same
• None of the atoms in alkanes have any significant charge
• Neither nucleophiles nor electrophiles are attracted
Alkanes are very unreactive → Paraffins (from Latin parum affinis –
‘little affinity’)
Most useful reactions of alkanes (halogenation, combustion, cracking..)
take place under energetic or high-temperature conditions

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HALOGENATION OF ALKANES
Take place only at high temperatures or in the presence of light

Chlorination and bromination are the most widely used.

Fluorine is an extremely aggressive oxidizing agent, and its reaction with alkanes is strongly
exothermic and difficult to control.
The reaction of iodine with alkanes is endothermic and therefore exceedingly slow, even at
500oK (L)
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Mechanism: radical substitution (SR)
3 steps: initation, propagation and termination

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Chlorination versus Bromination
Chlorination is faster than bromination.
Chlorination is unselective, yielding a mixture of products
Bromination is often selective, yielding one major product

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Product distribution depends on two factors
◦ Probability: the number of H that can be abstracted that will lead to the
formation of the particular product
◦ Reactivity: The relative rate at which a particular H is abstracted

The more stable the radical, the more easily it is formed, the higher reactivity.

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Relative rates of alkyl radical formation by a chlorine radical at room temperature

Relative rates of alkyl radical formation by a bromine radical at 125oC

In bromination, the differences in reactivity are so great that the reactivity factor is
vastly more important than the probability factor → the major product of
bromination resulted from the abstraction of H from highest substituted Carbon.

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STEREOCHEMISTRY

the incoming halogen has equal

access to both sides of the plane
→ both the R and S enantiomers
are formed

the reaction is
not stereoselective.
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Radical Substitution of Benzylic and Allylic Hydrogens

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2.11. Dự đoán tất cả những sản phẩm chủ yếu có thể hình thành của các phản ứng
sau đây, bao gồm các đồng phân lập thể với công thức chiếu Fisher hoặc công thức
không gian ba chiều

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f)

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S.15.51. Draw the products formed in each reaction and include the
stereochemistry around any stereogenic centers

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2.11. Dự đoán tất cả những sản phẩm chủ yếu có thể hình thành của các phản ứng
sau đây, bao gồm các đồng phân lập thể với công thức chiếu Fisher hoặc công thức
không gian ba chiều

f)

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 2.12. Xác định tất cả các đồng phân chủ yếu có thể hình thành của các phản ứng
sau đây, bao gồm các đồng phân lập thể với công thức chiếu Fisher hoặc công thức
không gian ba chiều:

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2.14. Khi thực hiện phản ứng thế một lần giữa đồng phân (S)-2-bromppentane với Br2 ở
nhiệt độ 125 oC để hình thành các sản phẩm 2,3-dibromopentane. Trong các đồng phân
sau đây, đồng phân nào không phải là sản phẩm từ phản ứng nói trên? Giải thích?

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2.18. Hoàn thành các chuỗi phản ứng sau đây (tính cả các đồng phân lập thể nếu có):

a)

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