ALLEN CAREER INSTITUTE

ASHOKNAGAR_CHENNAI

Section: Jr IIT Reaction Drill

Name of the student: HYDROCARBONS CPR Sir

ALKANES
Preparation:
1. Hydrogenation
a. H2/Ni or Pt-C or Pd or PtO2 – alkenes and alkynes, when Ni is used Sabatier-Sanderen reaction - SYN
b. Wilkinson’s Catalyst: H2/(Ph3P)3RhCl – homogeneouscatalysis –alkenes (mainly) and alkynes - SYN
c. Hydroboration of alkenes by B2H6 followed by acidification – SYN
d. Dimide: HN=NH or N2H4-H2O2 –alkenes as well as alkynes- SYN
2. Hydrogenolyis of RX
a. LiAlH4
 Mech: SN2
 As it is a strong base elimination may compete if 3° RX are used
 Reduces all type of alkyl halides including vinylic, bridgehead and cyclopropyl halides.
 Not selective as it reduces functional groups like COOH, COOR,CN, -CO- etc.
b. NaBH4
 Mech: SN1 mainly in diglyme (MeOCH2CH2OCH2CH2OMe)
 Can reduce 2° and some 3° RX selectively without affecting functional groups like COOH,COOR,CN which
are in general reduced by LiAlH4
c. Activated metals like raney nickel, PtO2 etc can also reduce alkyl halides
d. Bu3SnH or Ph3SnH reduces selectively C-X bond without affecting other functional groups
 Does by free radical mechanism
Following reagents reduce by electron transfer (believed to be by nascent H earlier)
e. Na/ROH; Zn-Cu couple/EtOH
f. Zn-NaOH; Devarda’s alloy (Zn-Al-Cu)/NaOH
g. Zn/AcOH
h. Mg or Al amalgam/H2O
i. Red P - HI
3. From RX
a. Reaction with Magnesium in dry ether followed by reaction with any compound that is more acidic than
alkane(pKa ≈ 50)
 Alkenes don’t give alkanes on reaction with RMgX
 Allyl, benzyl and propargyl hydrogens are also not abstracted by RMgX.
 Simple aldehydes and ketones don’t give alkanes with RMgX as they undergo kinetically favourable
nucleophilic addition
b. Wutrz reaction
 Mech: SN2 (mainly)

By-products
  Free radical Mechanism may be involved under some conditions (Couldn’t get an example…)
RCH2CH2X + Na  RCH2CH2∙ + NaX
2 RCH2CH2∙  RCH2CH2CH2CH2R
By-products can be explained by disproportionation of radicals.
RCH2CH2∙ + RCH2CH2∙  RCH2CH3 + RCH=CH2
 3° RX gives alkene as the main product.
 Reactivity: RI>RBr>RCl
 Intramolecular reactions : formation of cycloalkanes
c. Corey House Synthesis
Mech: SN2 mainly
RX + R’2CuLi→ R-R’
R = 1°, allylic or benzylic
R’ = 1°, 2°, 3° allylic, vinylic or aryl
d. Frankland reaction
2RX + Zn/EtOH→ R-R + ZnX2
R can be 1°, 2°, 3° allylic, vinylic or aryl
4. From Alcohols
a. By Red P/HI
b. TsCl/LiAlH4 – SN2
5. From Carbonyl compounds
a. HI/Red P
 Can convert aldehydes, ketones, acids and even alcohols into corresponding alkanes.
b. HS(CH2)3SH/BF3; H2/Pd
c. Clemmensen’s reduction:
 Zn-Hg/Con.HCl converts aldehydes and ketones into corresponding alkanes.
 Mech: uncertain but alcohol is not an intermediate
 Pinacol is often the by-product.
Carbenoid mechanism

 Cannot be used with acid sensitive groups like C=C, C≡C, etc.
d. Wolf-Kishner Reduction
 NH2NH2/NaOH-glycol reduces aldehydes and ketones in to corresponding alkanes.
 Mech: Refer Class notes
 Cannot be used with base sensitive groups like hemiacetal.
 Highly sterically hindered ketones are reduced by vigorous treatment with anhydrous hydrazine.
6. From Carboxylic acids:
a. Decarboxylation
 Carbanion mech when soda lime is used
 Chelation mechanism when β-keto acids are heated
 EAS during acid catalysed decarboxylation of aromatic acids.
b. Kolbe’s Electrolysis
  Byproducts
c. HI/Red P
7. Misc
a. From Al3C4 & Be2C by hydrolysis
b. Berthelot synthesis
C + H2 heat in electric arc – mixture of CH4, C2H6
Physical Properties:
a. State
b. Boiling point
c. Melting point
Effect of branching on MP: in general branching increases the MP but not always.

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Reactions:
1. Free radical Substitution
Steps: Initiation
Propagation
Termination
Inhibition
Reactivity:
F2>Cl2>Br2>I2
1° : 2° : 3°
Cl 1 : 3.8 : 5 at 25°C
Br 1 : 82 : 1600 at 127°C
Selectivity: I2>Br2>Cl2>F2
Iodination of methane is effected in presence of an oxidizing agent like HNO 3, HIO3 or HgO as the reaction is
reversible.
Stereochemistry : racemisation
Allyl susbttiution: X2/∆; SO2Cl2/∆ or light; NBS; ROCl/∆ or light
2. Vapour phase nitration (673 K – 773 K):
 Mixture of products are obtained
 Synthetically not useful
3. Sulphonation (>5 carbons only)
4. With steam (Ni, 1273 - water gas formation)
5. Isomerization with AlCl3/HCl at 573 K
 Branching increases as alkanes are heated with AlCl 3/HCl – bridged carbocation
6. Aromatization
 n-hexane can be converted in to benzene by any one of the following catalysts.
a. Cr2O3-Al3O3 – 873 K
b. Cr2O3-Pt – 873 K
c. Mo2O3
d. V2O5
7. Reforming
  Chemical process used to convert petroleum distilled from crude oil (typically having lowoctane ratings) into high-
octane liquid products. The process converts low-octane linear hydrocarbons (paraffins) into branched alkanes
(isoparaffins) and high-octane aromatic hydrocarbons.
The processes which take place during reforming are, dehydrogenation, aromatization, isomerization and cracking.
8. Heat of combustion and Stability
 Isomeric alkanes with more branching have lesser heat of combustion and hence higher stability.
9. Oxidation of alkanes:

a. CH4 + O2  CH3OH

Cu ,473 K ,100 atm

b. RCH3 + O2  RCOOH

Mn ( OAc ) 2 , heat

c. Me3CH  Me3COH

alk KMnO4

10. Misc
a. Pyrolysis of methane at 1273 K carbon black
b. With nitrogen in presence of electric arc methane gives HCN and H 2
Reactions of Cyclopropane – ring opening
ALKENES
Preparations
1. From Alkanes
a. Cracking
b. Catalytic dehydrogenation
2. From Alkynes
a. Lindlar’s catalyst – Syn Addition
b. P-2 Catalyst – Syn Addition
c. Sia2BH/AcOH – Syn Addition
d. Na/liq.NH3 – Anti Addition
 Not to be used for reduction of terminal alkynes as they give acetylides.
3. From RX:
 E2 Mechanism
 Single step mechanism
 Strong bases like alcoholic KOH, R3N etc are used.
 Takes place at high temperatures
 Rate = k[RX][base]
 Kinetic isotope effect for both β-H and leaving group
 Reactivity of RX: 3°>2°>1°; RI>RBr>RCl>RF
 Orientation: Zaitsev’s – more substituted alkene – more stable alkene
 Extended Conjugation
 Elemental effect – Hoffman product in case of fluorides
 Steric hinderance – bulky bases like t-BuOK
 Bredt’s rule – double bonds are not formed at bridge heads
 Endo cyclic double bonds are more stable than exocyclic by about 0.5 kcal in five and six
membered rings
 Stereoshemistry: Anti periplanarity
 E1 Mechanism
 Two step mechanism, involves carbocation formation
 Rate = k[RX]
 Weak base like solvent favours it by disfavouring E2.
 Alkyl halides having no β hydrogen may follow E1 in presence of strong base as well
  Takes place at high temperatures
 Reactivity of RX: 3°>2°>1°; RI>RBr>RCl>RF
 Orientation : Zaitzev’s
 E1CB Mechanism
 Occurs when β-H is acidic and leaving group is poor.
 Involves carbanion intermediate

 E1cb(rev)
 Rate = k[RX][base]
 Exchange of β-H with protic solvent
 E1cb(irr)
 Rate = k[RX][base]
 Leaving group effect: F>Cl>Br>I
4. From dihalides – E2
a. Zn dust/AcOH – Anti elimination
b. NaI/Acetone
 Anti elimination
 With dibromides or dichlorides, one of the halide gets substituted first by I - (SN2) and then dehalogenation
takes place if at least one of the halogen is attached to a primary carbon which results in the
diastereomer of the expected alkene.
5. From Alcohols
 Con.H2SO4, Con.H3PO4, SOCl2, PX3, Al2O3, ThO2, KHSO4, PCl5, P4O10 are the common catalysts used for
dehydration.
 With 2° & 3° alcohols the mechanism is E1 and with 1° the mechanism is E2
 As H3PO4 prevents charring of the organic product formed, it is preferred over H 2SO4. KHSO4 too scores better
than H2SO4 for the same reason.
 SOCl2, PCl5 and PX3 convert OH group in to better leaving group and thereby promote dehydration.
 Al2O3 gives more substituted product with rearrangement as the major product(>90%).
 Al2O3 – pyridine: Zaitvev’s product without rearrangement
 ThO2 gives principally less substituted(>90%) product – No rearrangement.
6. Wittig Reaction – ylide – betaine – oxaphosphetane
Reaction of ylide with oxirane - stereochemistry
7. Kolbe’s electrolysis
8. Hoffman degradation
 Mech: E2
 Hoffman orientation
 Mostly Anti elimination
9. Ei mechanisms
a. Cope elimination
 Involves five membered transition state
 Syn elimination
 Hofmann orientation
b. Pyrolysis of esters/xanthates
 Involves six membered transition state
  Syn elimination
 Hofmann orientation
Reactions of Alkenes
1. Isomerization
2. Hydrogenation – Syn addition
Reactivity
3. Addition of HX
 Involves carbocation
 Reactivity
 Regiochemistry – Markownikoff’s orientation
 Rearrangement is common
 Stereochemistry – Attack by electrophile as well as nucleophile are on sp 2 carbon – All possible stereoisomers
– non-stereoselective
4. Addition of HBr in presence of Peroxide
 Involves free radicals
 Regiochemistry – anti Markownikoff’s orientation
 Observed only with HBr for thermodynamic reasons
5. Addition of X2
 Reactivity
 Stereo: Anti Addition mostly
6. Addition of X2/H2O
Regio: MK
Stereo: Anti mostly
 Addition of Br2/ROH – Intramolecular variant of the same
7. Addition of water
Regio : Mk
Stereo: Non-Stereoselective
8. Oxymercuaration – Demercuration
Ether formation with unsaturated alcohols (intramolecular)
9. Hydroboration – Oxidation
Regio: Hydroboration : MK
Overall :anti MK
Stereo: SYN
 Hydroboration – ammonolyis _NH2Cl - RNH2
 Hydroboration – acidolysis – RH
 Hydroboration – dimer alkylation – AgNO3 – R-R
10. Addition of cold con.H2SO4
11. Dimerization of alkenes
12. Halolactonization
13. Addition of alkanes to alkenes – Lewis acid or H + catalyst (-30 to 100°C) – mixture- done thermally as well (radical
mechanism at 500°C and 150 to 300 atm)
14. Misc AE
a. ICl– Regio: MK
b. NOCl– Regio: MK
c. RCl/AlCl3– Regio: MK
d. RCOCl/AlCl3 – Regio: MK
e. PhSCl – Regio: MK
 f. CHCl3/ROOR – Regio: aMK
15. Hydroxylations
a. Addition of cold dil.KMnO4 - Syn
b. OsO4-NaHSO3 or OsO4-H2O2 – Syn
c. Oxidative cleavage by Leumix reagent – KMnO 4 – NaIO4 – revise cleavage of diols and related compounds by
HIO4 or Pb(OAc)4
d. Epoxiation-Hydrolysis – Anti
 Cleavage of diols
16. Reaction with hot alk.KMnO4
17. Ozonolysis – reductive and oxidative
18. Allylic substitution – NBS – allylic rearrangement
19. Addition of carbenes
Reaction of pyrrole with CHCl3/KOH
Stereo: Singlet – stereoselective
Triplet - nonstereoselective
20. Simon-Smith reaction - carbenoid
21. Oxoprocess : Regio: MK of H- & CHO+
22. Wacker’s Process
Regio: Mk (Add H2O Mk way and oxidize it to corresponding ketone)
Ethylene gives acetaldehyde
23. Koch Process
Regio: Mk addition of H+ and CO followed by hydrolysis
24. Oxidation by SeO2 – Allyl alcohols

DIENES
Preparation
1. Wurtz reaction of allyl halides
2. From 1,2,3-trihalides: alc.KOH followed by dehalogenation with Zn
3. Dehydrogenation of alkanes: Cr2O3/Al2O3
4. Dehydrogenation of alkenes: Ni – Ca phosphate
5. Dehydration of allyl alcohol : KHSO4
Reactions of conjugated dienes
1. 1,2 and 1,4-addition: Kinetic and thermodynamic control
 H2
 Br2
 HBr
2. With Na/liq.NH3
3. Diels – Alder reaction
 Condition : mostly thermal, light induced are also known
 Predicting product
 Reactivity
 Regioselectivity
 Hetero Diels Alder reaction
4. Diels – Alder reaction
 Condition : mostly thermal, light induced are also known
 Predicting product
Reactions of Cummulene
1. Addition of HX
 2. Hydration
3. With Na/liq.NH3
ALKYNES
Preparation
1. Dehydrohalogenation of vic. Or gem dihalides
2. Dehalogenation of tetrahalides
3. From calcium carbide
4. Higher alkynes form ethyne
5. From RCHCl3
Reactions:
1. Addition of Electrophilic Reagents
a. Reactivity of alkene Vs alkyne
b. X2
c. HX
i. Addition of HCl to HC≡C-CH=CH2 to H2C=CH-C(Cl)=CH2 via CH2Cl-CH=C=CH2
Catalyst: CuCl & NH4Cl
d. X2/H2O
e. H2O/H+/Hg2+
f. ACOH/Hg2+
g. HBO
Di sec-isoamylborane (Me2CHCHMe)2BH or (siamyl)2BH
2. Hydrogenation
There are different opinions on the rates of hydrogenation of alkenes and alkynes. The most acceptable one seems to
be that hydrogenation of alkyne is faster than alkene. Two of the reasons sited by different books are:
(i) Hydrogenation of alkyne is more exothermic and hence is faster (Jerry March)
(ii) Adsorption of alkyne has more positive entropy of activation compared to alkenes. Alkenes are adsorbed on the
surface of the catalyst only when the plane of the pi bond approaches perpendicularly. Because of the cylindrical
nature of the pi bonds of alkynes, any approach along the axis of the cylinder can be successful. These less
constrained transition states cause alkynes to have more positive entropy of activation values. (Schaums series)
3. Oxidation
a. Cold dil.alk.KMnO4
b. Hot alk/acidic KMnO4
4. Ozonolysis
5. Acidity of terminal alkyne
a. Reaction with NaNH2
b. Reaction with Na
c. Reaction with Ammoniacal AgNO3
d. Reaction with Ammoniacal CuCl
6. Isomerization
a. With NaNH2
b. With alc.KOH
7. Poymerization
a. CuCl/NH4Cl
b. Fe or Cu tube
c. Ni(CN)4
d. EtCCEt with Si2Cl6
8. Nucleophilic additions
a. HCN/NaCN or Ba(CN)2....ie., catalytical quantities of CN-
b. ROH/KOH
9. Reaction of acetylene
a. Cl2/H2O (1 equiv)
b. Cl2/H2O (2 equiv)
c. Cl2/H2O (excess)
d. HC≡CH + NaOCl gives ClC≡CCl at 273 K
e. HC≡CH + I2 gives IC≡CI at 273 K
f. EtOCH2Cl in presence of AlCl3
g. RCOCl in presence of AlCl3
h. AsCl3 – Lewisite (vesicant – blister agent)
i. Prep of Westrosol CHCl=CCl2
j. Mustard Gas : SCl2 + C2H4 gives ClCH2CH2SCH2CH2Cl – war gas
k. Preparation of neoprene from acetylene
l. NH3 – pyrrole
m. S – thiophene