Saya Minn Thant ORGANIC CHEMISTRY FOR MATRICULATION STUDENTS Summary

Alkanes
Preparations of Alkanes

(1) Heating sodium salt of carboxylic acid with soda lime

R-COONa + NaOH CaO R-H + Na2CO3
sodium alkanoate alkane

(2) Reduction of alkyl halides

i. with hydrogen halide (Hydrohalogenation)

R-X + HX → R-H + X2
alkyl halide alkane
ii. with hydrogen using platinum(Pt) or palladium(Pd) catalyst
(Hydrogenation)
𝑃𝑡 𝑜𝑟 𝑃𝑑
R-X + H2 → R-H + HX
alkyl halide alkane
(3) Reduction of alkene with hydrogen
(Hydrogenation)
R-CH=CH2 + H2 𝑁𝑖,3000 𝐶 R-CH2-CH3
→
Alkene alkane

Chemical Properties of Alkanes

(1) Combustion of alkanes

∆
R-H + O2 → CO2 + H2O
alkane

(2) Chlorination of methane (Substitution reaction)

CH4 + Cl2 → CH3Cl CH2Cl2 → CHCl3 → CCl4
methane methyl methylene chloroform carbon
chloride chloride tetrachloride
diffused sunlight

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Saya Minn Thant ORGANIC CHEMISTRY FOR MATRICULATION STUDENTS Summary

Alkenes
Preparations of Alkenes

(1) Dehydration of alcohol

i. Heating alcohol with concentrated sulphuric acid at 1600C
Two stages
0𝐶
R-CH2-CH2OH + H2SO4 100
→
R-CH2-CH2SO4H + H 2O
alcohol alkyl hydrogen
sulphate

R-CH2-CH2SO4H 1600 𝐶
→ R-CH=CH2 + H2SO4
alkene
One stage
𝑯𝟐 𝑺𝑶𝟒 (𝒄𝒐𝒏𝒄)
R-CH2-CH2OH → R-CH=CH2 + H 2O
alcohol 1600 𝐶 alkene
ii. passing alcohol vapour over alumina catalyst heated at 3500C
𝑨𝒍𝟐 𝑶𝟑
R-CH2-CH2OH → R-CH=CH2 + H 2O
𝟎
alcohol 𝟑𝟓𝟎 𝑪 alkene
(2) Dehydrohalogenation of alkyl halide
ethanol
R-CH2-CH2X + KOH R-CH2=CH2 + KX + H2O
alkyl halide alkene

Chemical Properties of Alkenes

(1) Combustion of alkenes
∆
R-CH=CH2 + O2 → CO2 + H2O
alkene
(2) Addition reaction
i. Hydrogenation (Addition of hydrogen)
R-CH=CH2 + H2 →𝑁𝑖,200−3000𝐶 R-CH2-CH3
alkene alkane
ii. Halogenation (Addition of halogen)
R-CH=CH2 + X2 → R-CHX-CH2X
alkene alkene dihalide

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Saya Minn Thant ORGANIC CHEMISTRY FOR MATRICULATION STUDENTS Summary

iii. Hydrohalogenation (Addition of alkyl halide or halogen acid)

(a) Symmetrical alkenes
CH2=CH2 HX → CH3-CH2X
ethene (symmetrical) ethyl halide
(b) Unsymmetrical alkenes
CH3-CH=CH2 + HX → CH3-CX-CH3 + CH3-CH2-CH2-X
propene iso-propyl halide n-propyl halide
(unsymmetrical) (major product) (minor product)
(3) Ozonolysis (Formation of ozonide)
O
𝑐ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚
CH2=CH2 + O3 → CH2 CH2
O O
ethene ethene ozonide
O
𝑍𝑛 𝑑𝑢𝑠𝑡
CH2 CH2 + H2O → 2HCHO + H 2O 2
O O
ethene ozonide methanal
(formaldehyde)
(4) Hydroxylation
R-CH=CH2 + H2O + [O] 𝑐𝑜𝑙𝑑 𝑑𝑖𝑙𝑢𝑡𝑒 R-CHOH-CH2OH
alkene 1%𝐾𝑀𝑛𝑂4 alkene glycol
(violet) (colourless)
(5) Polymerization
n(CH2=CH2) > 1000 𝑎𝑡𝑚 ( CH2-CH2 ) n
ethene ∆ polyethene
(monomer) (polymer)

....................................................................................................................
Alkynes
Preparations of Alkynes
(1) Laboratory method to prepare ethyne or acetylene from coke
CaO + 3C 𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐 CaC2 + CO
coke 𝑓𝑢𝑟𝑛𝑎𝑐𝑒 calcium
carbide
CaC2 + 2H2O Ca(OH)2 + CH CH
ethyne

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Saya Minn Thant ORGANIC CHEMISTRY FOR MATRICULATION STUDENTS Summary

(2) Dehydrohalogenation of alken dihalide or alkylidene halide

𝑒𝑡ℎ𝑎𝑛𝑜𝑙
R-CHX-CH2X + 2KOH ∆ R-C CH + 2KX + 2H2O
alkene dihalide alkyne
𝑒𝑡ℎ𝑎𝑛𝑜𝑙
R-CH2-CHX2 + 2KOH ∆ R-C CH + 2KX + 2H2O
alkylidene halide alkyne

Chemical Properties of Alkynes

(1) Addition reaction
i. Hydrogenation or reduction
CH≡CH + H2 CH2=CH2 + H2 CH3-CH3
ethyne Pt or Pd ethene Pt or Pd ethane
ii. Halogenation
CH≡CH + Cl2 𝑙𝑖𝑔ℎ𝑡 CHCl=CHCl
ethyne 𝑚𝑒𝑡𝑎𝑙𝑙𝑖𝑐 ℎ𝑎𝑙𝑖𝑑𝑒 ethyne dichloride

CHCl=CHCl + Cl2 𝑙𝑖𝑔ℎ𝑡 CHCl2 - CHCl2

ethyne dichloride 𝑚𝑒𝑡𝑎𝑙𝑙𝑖𝑐 ℎ𝑎𝑙𝑖𝑑𝑒 ethyne tetrachloride
Notes; Br(aq) has only one stage
iii. Hydrohalogenation
CH≡CH + HBr CH2=CHBr
ethyne vinyl bromide
(symmetrical)
CH2=CHBr + HBr CH3-CHBr2
vinyl bromide ethylidene bromide
(unsymmetrical)
iv. Hydration
CH≡CH + H2O 𝐻2 𝑆𝑂4 , 600 𝐶 CH2=CHOH CH3-CHO
𝐻𝑔++
ethyne vinyl alcohol ethanal
(unstable)
(2) Substitution reaction
i. sodium
∆
CH≡CH + Na CH≡C-Na + 1
2
H2
ethyne monosodium acetylide
∆
CH≡C-Na + Na Na-C≡C-Na + 1
2
H2
monosodium disodium acetylide
acetylide

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 Saya Minn Thant ORGANIC CHEMISTRY FOR MATRICULATION STUDENTS Summary

ii. With ammoniacal copper (I) chloride solution

2CH≡CH + Cu2Cl2 + 2NH3 2CH≡C-Cu ↓ + 2NH4Cl
acetylene monocopper (I)
acetylide
(red p.p.t)

2CH≡C-Cu + Cu2Cl2 + 2NH3 2Cu-C≡C-Cu ↓ + 2NH4Cl

monocopper dicopper acetylide
acetylide (red p.p.t)

2CH3-C≡CH + Cu2Cl2 + 2NH3 2CH3-C≡C-Cu ↓ + 2NH4Cl

methyl acetylene copper (I) methyl
(propyne) acetylide
(red p.p.t)

2CH3-CH2-C≡CH + Cu2Cl2 + 2NH3 2CH3-CH2-C≡C-Cu ↓ + 2NH4Cl

ethyl acetylene copper (I) ethyl acetylide
(1-butyne) (red p.p.t)

CH3-C≡C-CH3 + Cu2Cl2 + 2NH3 no reaction

dimethyl acetylene (no p.p.t)
(2-butyne)

iii. With ammoniacal silver oxide solution

2CH≡CH + Ag2O + NH3 2CH≡C-Ag↓ + NH4OH

acetylene monosilver acetylide
(ethyne) (white p.p.t)

2CH≡C-Ag + Ag2O + NH3 2Ag-C≡C-Ag ↓ + NH4OH

monosilver disilver acetylide
acetylide (white p.p.t)

2CH3-C≡CH + Ag2O + NH3 2CH3-C≡C-Ag ↓ + NH4OH

methyl acetylene silver methyl
(propyne) acetylide
(white p.p.t)

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 Saya Minn Thant ORGANIC CHEMISTRY FOR MATRICULATION STUDENTS Summary

2CH3-CH2-C≡CH + Ag2O + NH3 2CH3-CH2-C≡C-Ag ↓ + NH4OH

ethyl acetylene silver ethyl acetylide
(1-butyne) (white p.p.t)

CH3-C≡C-CH3 + Ag2O + 2NH3 no reaction

dimethyl acetylene (no p.p.t)
(2-butyne)

Special Notes;

CH3-CH3 CH3-CH2Cl CH3-CHCl2

ethane ethyl chloride ethylidene chloride
CH2Cl-CH2Cl
ethene dichloride
CH3-CH2-CH3 CH3-CH2-CH2Cl CH3-CH2-CHCl2
propane n-propyl chloride n-propylidene chloride
CH3-CHCl-CH3 CH3-CCl2-CH3
iso-propyl chloride iso-propylidene chloride
CH3-CHCl-CH2Cl
propylene dichloride
CH2=CH2 CH2=CHCl
ethene ethenyl chloride
(vinyl chloride)

CH3-CH=CH2 CH3-CH=CHCl
propene n-propenyl chloride
(2-methyl vinyl chloride)
CH3-CHCl=CH2
iso-propenyl chloride
(1-methyl vinyl chloride)

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Saya Minn Thant ORGANIC CHEMISTRY FOR MATRICULATION STUDENTS Summary

Alcohols
Preparations of Alcohols
(1) Hydrolysis of alkyl halide
R-CH2X + NaOH reflux R-CH2OH + NaX
alkyl halide alkyl alcohol

(2) Hydrolysis of alkyl hydrogen sulphate

R-CH2-SO4H + H2O reflux R-CH2OH + H2SO4
alkyl alkyl alcohol
hydrogensulphate
(3) Manufacture of ethanol from petroleum refinery products
5200 𝐶,12 𝑎𝑡𝑚
hydrocarbon → Alkanes + ethene
(very high (C5H12 to C9H20) (by product)
molecular weight)
CH2=CH2 + H2SO4 CH3-CH2SO4H
Ethene ethyl hydrogensulphate
CH2=CH2 + CH3-CH2SO4H (CH3-CH2)2 SO4
ethene diethyl sulphate
CH3-CH2SO4H + H2O CH3-CH2OH + H2SO4
ethyl ethanol
hydrogensulphate
(CH3-CH2)2 SO4 + 2H2O 2CH3-CH2OH + H2SO4
diethyl sulphate ethanol

(4) Manufacture of ethanol by fermentation (fermentation method)

n diastase 𝑛
(C6H10O5)n + H2O → C12H22O11
2 2
starch maltose

+ H2O Yeast (maltase)

2CH3-CH2OH + 2CO2 yeast (zymase) C6H12O6

ethanol glucose
Chemical properties of Alcohols
(1) Reaction with metallic sodium
R-CH2OH + Na R-CH2ONa + 1
H2
alcohol sodium alkoxide 2

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Saya Minn Thant ORGANIC CHEMISTRY FOR MATRICULATION STUDENTS Summary

(2) Reaction with phosphorous (V) oxide, PCl5

R-CH2OH + PCl5 𝑎𝑡 𝑟𝑜𝑜𝑚 R-CH2Cl + POCl3 + HCl
𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
alcohol alkyl chloride
(3) Reaction with sulphuric acid
0𝐶
R-CH2-CH2OH + H2SO4 100
→
R-CH2-CH2SO4H + H 2O
alcohol alkyl hydrogen
sulphate

R-CH2-CH2SO4H 1600 𝐶
→ R-CH=CH2 + H2SO4
alkene

CH3-CH2OH + H2SO4 1000 𝐶 CH3-CH2SO4H + H2O

ethanol ethyl hydrogen
sulphate
CH3-CH2OH + CH3-CH2SO4H 1400 𝐶 CH3-CH2-O-CH2-CH3 + H2SO4
ethanol diethyl ether
(4) Formation of ester (esterification)
i. Inorganic ester
CH3-CH2OH + H2SO4 CH3-CH2SO4H + H2O
ethanol ethyl hydrogen
sulphate
(inorganic ester)
ii. Organic ester
𝐻2 𝑆𝑂4 (𝑐𝑜𝑛𝑐)
CH3-COOH + CH3-CH2OH CH3-COO-CH2-CH3 + H2O
𝐻+
ethanoic acid ethanol ethyl ethanoate
(ethyl acetate)
(organic ester)
(5) Oxidation of alcohols
i. Dehydrogenation with copper at 3000C
CH3-CH2OH 𝐶𝑢, 3000 𝐶 CH3-CHO + H2
ethanol ethanal
(vapour)
ii. Oxidation with acidified K2Cr2O7
CH3-CH2OH + [O] 𝐾2 𝐶𝑟2 𝑂7 CH3-CHO + H2O
ethanol 𝐻2 𝑆𝑂4 (𝑑𝑖𝑙) ethanal
CH3CHO + [O] 𝐾2 𝐶𝑟2 𝑂7 CH3COOH
ethanal 𝐻2 𝑆𝑂4 (𝑑𝑖𝑙) ethanoic acid

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