CC2/GE 2: Syllabus

SEM-II General: Organic Chemistry Dr Harisadhan Ghosh Department of Chemistry, Surendranath College ______

CC2/GE 2: Syllabus

Functional group approach for the following reactions (preparations & reactions) to be studied in context to their structures.

Alkanes: (up to 5 Carbons). Preparation: catalytic hydrogenation, Wurtz reaction, Kolbe’s synthesis.

Alkenes: (up to 5 Carbons). Preparation: elimination reactions: dehydration of alcohols and dehydrohalogenation of alkyl halides; cis alkenes (partial catalytic hydrogenation) and trans alkenes (Birch reduction). Reactions: addition of bromine, addition of HX [Markownikoff’s (with mechanism) and anti- Markownikoff’s addition], hydration, ozonolysis.

Alkynes: (up to 5 Carbons). Preparation: acetylene from CaC2; by dehalogenation of tetra halides and dehydrohalogenation of vicinal dihalides.

Aliphatic Hydrocarbon: Alkanes Introduction:

Open chain binary compounds of C and H containing C-C and C-H s-bonds only, are called alkanes. Since there is no C-C multiple bond, alkanes are saturated hydrocarbons. Alkanes are represented as R-H or R-

R’ or R-CH3 etc. where R, R’ are alkyl groups. For examples, propane may be represented as R-H (R= - CH2CH2CH3) or R-CH3 (R= -CH2-CH3). The main sources of alkanes are natural gas and petroleum oil.

Chemical Reaction of Alkanes:

As the C—C and C—H bonds are quite strong: alkanes are generally inert to many chemical reagents. The C—H bonds of alkanes are only slightly polarized, so alkanes are generally unaffected by most bases. Alkane molecules have no unshared electrons to offer sites for attack by acids. That is why alkanes are known as Paraffins (Latin: parum affinis, little affinity).

General Reactivity of Alkanes:

1) Alkanes react vigorously with oxygen when an appropriate mixture is ignited. It is known as combustion. 2) Alkanes react with chlorine and bromine when heated, and they react explosively with fluorine.

@HG Sir, SNC Synthesis of Alkanes:

1. Catalytic Hydrogenation: Alkenes and alkynes react with hydrogen in the presence of metal catalysts such as nickel, palladium, and platinum to produce alkanes. General Reaction

C H Pt, Pd, or Ni C H C Pt, Pd, or Ni H C H + + 2 H2 C H solvent, C H C solvent, H C H pressure pressure

Alkene Alkane Alkyne Alkane

The reaction is usually carried out by dissolving the alkene or alkyne in a solvent such as ethyl alcohol 498 TABLE OF CONTENTS PREVIOUS REACTION NEXT REACTION SEARCH TEXT (C2H5OH), adding the metal catalyst, and then exposing the mixture to hydrogen gas under pressure in a special apparatus. WURTZ COUPLING Specific Examples (References are on page 713) Importance: Ni CH3CH CH2 + H H C1,2H3CH C3-7H2 8-16 [SeminalC2H5O PublicationsH ; Reviews ; Modifications & Improvements ] (25 oC, 50 atm) H H propeneIn 1855, A. Wurtz treated alkyl halides with sodiumprop metaane l, and he isolated the corresponding symmetrical alkane dimers.1,2 The coupling of two sp3-carbon centers by the treatment of alkyl or benzyl halides with sodium metal is known as the Wurtz coupling . When metals other than sodium are used, this transformation is referred to as a Wurtz- CHtype3 coupling. The coupling of an alkyl and an arylC Hhalide3 in the presence of sodium metal to get the corresponding alkylated aromatic compoundN i is called the Wurtz-Fittig reaction. Today, the synthetic significance of the Wurtz H3C C couplingCH2 +is HfairlyH limited and often in widelyH3C usedC reactionsCH2 (e.g., Grignard reactions) involving highly reactive C2H5OH organometals, such as( 2allyl-5 oC ,and 50 abenzylmetals,tm) thisH is Hthe side reaction. The general features of the Wurtz coupling are: 1) the classical reaction is heterogeneous and relatively low-yielding, because it is plagued by side reactions 2-Methylpropene Isobutane such as elimination and rearrangements; 2) best results are achieved with finely dispersed sodium metal; 3) alkyl halides can be coupled both inter- and intramolecularly; 4) the order of reactivity for alkyl halides is: I >> Br >> Cl, and by far primary alkyl iodides areNi the best substrates; 5) secondary alkyl halides are generally poor substrates and should be avoided;+ H 26) the method works reasonably well for intermolecular homocouplings, but the heterocoupling of two different alkyl halides C often2H5O resultsH in a statistical mixture of products in low yields; 7) intramolecularly, the o coupling can give rise to( 2strained5 C, 50 rings atm) as well as macrocycles (e.g., cyclopropanes, cyclobutanes, and cyclophanes) Cyclohexene Cyclohexane 17,4 in moderate to good yield, and it has been applied extensively for the preparation of such compounds; and 8) the Wurtz-Fittig reaction gives high yields of the desired product without significant side reactions mainly because aryl halides do not usually dimerize under the reaction conditions. Because of the limited synthetic value of the classical 2. Wurtz reaction reaction conditions, several modifications were introduced: 1) the most widespread reaction condition (Müller modification) is to treat the alkyl halide with sodium metal in THF at -78 °C in the presence of catalytic amounts of tetraphenylethylene (TPE), which solubilizes the sodium and makes the reaction homogeneous; 8 2) metals other than sodium18 as well as various metal complexes have been used successfully to improve the yields and suppress 13 15 10 16 It is a metal mediated organicside coupling reactions: reaction activated where Cu, alkyl Mn 2halide(CO)10s, are Li coupledmetal/ultrasound, (joined) inNa(Hg), the presence Na-K alloy, Zn; and 3) the use of sonication (ultrasound) in general improves3 the yield, since the metal becomes highly dispersed and as a result its of Na, Mg, or other reactive metals. The coupling11,12,14 of two sp -carbon centers by the treatment of alkyl or benzyl halides with sodiumreactivity metal increases. is known as the Wurtz coupling. Wurtz homocoupling (dimerization): Wurtz heterocoupling (cross-coupling):

R1 2 Na (metal) 1 Na (metal) 1 R 2 1 R 1 2 R R X solvent R X + R X solvent Symmetrical Unsymmetrical alkane alkane

+ homocoupled products Wurtz homocoupling (dimerization): Wurtz-Fittig reaction: Wurtz-type coupling:

Ar X metal Na (metal) R2 Ar R2 (finely divided) 1 + R1 X + R2 X R solvent solvent R2 X Alkylated arene Unsymmetrical alkane @HG Sir, SNC R1 = 1° alkyl, aryl; R2 = 1° alkyl, aryl; Ar = electron-rich and electron-poor substituted aryl; metal = K, Mg, Zn, Cu etc.;

solvent = THF, Et2O, dioxane, xylenes

Mechanism: 19-30

The mechanism of the Wurtz coupling is not well understood, and the currently accepted mechanism involves two steps: 1) formation of a carbanionic organosodium compound via metal-halogen exchange; and 2) the displacement of the halide ion by the organosodium species in an SN2 reaction. Alternatively, a radical process can also be envisioned, although to date there has been no experimental evidence to support this assumption.

H2 Step #1: C R1 CH Na R1 X + 2 Na 2 + NaX organosodium

1 R1 R X S 2 1 Step #2: C N R R1 CH Na + NaX 2 H2 Symmetrical alkane 498 TABLE OF CONTENTS PREVIOUS REACTION NEXT REACTION SEARCH TEXT

WURTZ COUPLING (References are on page 713) Importance:

[Seminal Publications1,2; Reviews3-7; Modifications & Improvements8-16]

In 1855, A. Wurtz treated alkyl halides with sodium metal, and he isolated the corresponding symmetrical alkane dimers.1,2 The coupling of two sp3-carbon centers by the treatment of alkyl or benzyl halides with sodium metal is known as the Wurtz coupling. When metals other than sodium are used, this transformation is referred to as a Wurtz- type coupling. The coupling of an alkyl and an aryl halide in the presence of sodium metal to get the corresponding alkylated aromatic compound is called the Wurtz-Fittig reaction. Today, the synthetic significance of the Wurtz coupling is fairly limited and often in widely used reactions (e.g., Grignard reactions) involving highly reactive organometals, such as allyl- and benzylmetals, this is the side reaction. The general features of the Wurtz coupling are: 1) the classical reaction is heterogeneous and relatively low-yielding, because it is plagued by side reactions such as elimination and rearrangements; 2) best results are achieved with finely dispersed sodium metal; 3) alkyl halides can be coupled both inter- and intramolecularly; 4) the order of reactivity for alkyl halides is: I >> Br >> Cl, and by far primary alkyl iodides are the best substrates; 5) secondary alkyl halides are generally poor substrates and should be avoided; 6) the method works reasonably well for intermolecular homocouplings, but the heterocoupling of two different alkyl halides often results in a statistical mixture of products in low yields; 7) intramolecularly, the coupling can give rise to strained rings as well as macrocycles (e.g., cyclopropanes, cyclobutanes, and cyclophanes) in moderate to good yield, and it has been applied extensively for the preparation of such compounds;17,4 and 8) the Wurtz-Fittig reaction gives high yields of the desired product without significant side reactions mainly because aryl halides do not usually dimerize under the reaction conditions. Because of the limited synthetic value of the classical reaction conditions, several modifications were introduced: 1) the most widespread reaction condition (Müller modification) is to treat the alkyl halide with sodium metal in THF at -78 °C in the presence of catalytic amounts of tetraphenylethylene (TPE), which solubilizes the sodium and makes the reaction homogeneous; 8 2) metals other than sodium18 as well as various metal complexes have been used successfully to improve the yields and suppress 13 15 10 16 side reactions: activated Cu, Mn2(CO)10, Li metal/ultrasound, Na(Hg), Na-K alloy, Zn; and 3) the use of sonication (ultrasound) in general improves the yield, since the metal becomes highly dispersed and as a result its reactivity increases.11,12,14

Wurtz homocoupling (dimerization): Wurtz heterocoupling (cross-coupling):

R1 2 Na (metal) 1 Na (metal) 1 R 2 1 R 1 2 R R X solvent R X + R X solvent Symmetrical Unsymmetrical alkane alkane

+ homocoupled products

Wurtz-Fittig reaction: Wurtz-typeWurtz coupling: heterocoupling (cross-coupling): Ar X metal Na (metal) R2 Ar R2 (finely divided) 1 + R1 X + R2 X R solventMechanism of the Wurtz Reaction solvent R2 X Alkylated arene Unsymmetrical alkane

R1 = 1° alkyl, aryl; TheR2 = 1° currently alkyl, aryl; Ar accepted = electron-rich mechanism and electron-poor of Wurtzsubstituted reaction aryl; meta linvolves = K, Mg, Zn, two Cu etc.; steps: (1) formation of a carbanionic organosodium compoundsolvent = THF,(RNa) Et2O, dioxane, via metal xylenes-halogen exchange; and (2) the displacement of the halide ion by the organosodium species in an SN2 reaction.

Mechanism: 19-30

H2 Step #1: C R1 CH Na R1 WhenX metals+ other2 Na than sodium are used for coupling, 2this transformation+ Na Xis referred to as a Wurtz- type organosodium coupling.

1 R1 R X S 2 1 Step #2: C N R R1 CH Na + NaX 2 H2 Symmetrical alkane

Wurtz type reaction of cetyl iodide with Mg in ether gives n-dotriacontane in good yield.

A Wurtz coupling between two alkyl halides with different alkyl groups is usually not very efficient. Such reactions give a statistical mixture of all three possible products. For example, Wurtz coupling of 1- iodobutane with 1-iodopropane gives equal amounts of n-octane (produced from two molecules of 1- iodobutane), n-heptane (from one molecule of 1-iodobutane and one molecule of 1-iodopropane), and n- hexane (from two molecules of 1-iodopropane).

1-Iodopropane

The other side products during Wurtz Reaction is the formation of alkene (if the starting material contains b- hydrogen).

@HG Sir, SNC 3. Kolbe’s Synthesis.

Kolbe’s electrolysis is basically a decarboxylative dimerization reaction which proceeds with radical reaction mechanism with the evolution of CO2. It is an electrolysis reaction i.e the reaction occurs at anodic and cathodic compartment. By this method, alkane can be prepared from the sodium or potassium salt of the corresponding carboxylic acid. The plausible mechanism is as follows-

Examples of Kolbe Reaction:

COOK Kolbe Electrolysis COOK KOOC

Kolbe Electrolysis

COOK

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@HG Sir, SNC