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Ullmann Coupling

Ullmann Coupling

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Shrianshu Manimaya
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173 views4 pages

Ullmann Coupling

Ullmann Coupling

Uploaded by

Shrianshu Manimaya
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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UM-DAE CBS CL 701 2024 28th August, 2024

Lab Report: Ullmann Coupling


Date : 28/8/2024 Name : Shrianshu Manimaya
Roll no : 0211547

Ullmann Reaction

− The Ullmann reaction, also known as Ullmann coupling, is a coupling reaction


between aryl halides. It traditionally uses copper as a catalyst, but palladium and
nickel can also be effective.

− This reaction is crucial for forming carbon-carbon bonds, which are essential in the
synthetic applications of organic chemistry.

Methods of Carbon-Carbon Bond Formation

− Acetylide Anions: Used in reactions to form carbon-carbon bonds.

− Diels-Alder Reaction: A (4+2) cycloaddition reaction that forms six-membered rings.

− Grignard Reaction (RMgX): Forms carbon-carbon bonds from carbonyl


compounds.

− Wittig Reaction: Forms carbon-carbon bonds from carbonyl compounds using


phosphonium ylides.

− Gilman Reaction (R-CuLi): Similar to the Ullmann reaction, it uses organocopper


reagents.

Role of Catalysts

Transition Metals: Catalysts like copper, palladium, and nickel are used to facilitate
efficient production of pharmaceuticals, polymers, and other synthetic materials by
reducing cost and waste.

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UM-DAE CBS CL 701 2024 28th August, 2024

Experimental Procedure

1. Synthesis of 1-Iodo-2-Nitrobenzene: The experiment begins with synthesizing 1-


iodo-2-nitrobenzene, which is then used in the Ullmann coupling reaction.

2. Copper-Catalyzed Coupling: The copper catalyst induces the coupling to form 2,2'-
dinitrobiphenyl.

Mechanism of the Ullmann Reaction

− Electrophilic Aromatic Substitution: The first part of the experiment involves an


electrophilic aromatic substitution, forming a diazonium tosylate intermediate.

− Carbon-Carbon Bond Formation: The second part involves forming a carbon-


carbon bond between substituted aromatic rings using a copper catalyst.

Detailed Mechanism

− Di-Substituted Biaryls: Formed by coupling nitro-substituted aryl halides with


excess copper at elevated temperatures.

− Active Species: A copper(I) compound undergoes oxidative addition with a second


equivalent of halide, followed by reductive elimination to form the aryl-aryl carbon
bond.

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UM-DAE CBS CL 701 2024 28th August, 2024

Laboratory Procedure

1. Preparation: 1-iodo-2-nitrobenzene (1 mmol), copper powder (3 mmol), and sand


(200 mg) are mixed in a test tube.

2. Heating: The mixture is heated in a sand bath to about 350°C until the reaction
proceeds.

3. Cooling and Mixing: The test tube is cooled to room temperature, and the solid
material is mixed.

4. TLC Analysis: A sample is taken for TLC (dichloromethane:hexane 30:70) to


identify components in the crude mixture.

5. Column Chromatography: The crude solid is mixed with DCM, and the supernatant
is used to run column chromatography with dichloromethane:hexane (30:70) and
dichloromethane:ethyl acetate (90:10) to separate fractions.

6. Evaporation and Yield Determination: The solvent is evaporated from the second
fraction to determine the yield of 2,2'-dinitrobiphenyl. The identity and purity are
confirmed by observing the melting point and using spectroscopic techniques.

Confirmatory Tests

− Melting Point: Observing the melting point helps confirm the identity and purity of
the synthesized 2,2'-dinitrobiphenyl.

− Spectroscopic Techniques: Further confirmation of the product's identity and purity.

Observations and Calculations:

− Weight of reactant(1-iodo-2-nitrobenzene): 271 mg


− Weight of product (2,2-dinitrobiphenyl): 178 mg
− Melting point of product: 168 °C (theoretical range: 167–169 °C)

1. Theoretical Yield:

Molecular weight of 1-iodo-2-nitrobenzene = 256.03 g/mol

Molecular weight of 2,2-dinitrobiphenyl = 244.17 g/mol

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UM-DAE CBS CL 701 2024 28th August, 2024

For 1 mmol of 1-iodo-2-nitrobenzene, theoretical yield of 2,2-dinitrobiphenyl is:

1 mmol × 244.17 mg/mmol = 244.17 mg

2. Percentage Yield: = (Weight of product/Theoretical Yield) × 100%

= (178/244.17)×100=72.9 %

Conclusion:

Therefore the percentage yield of Ullmann Coupling is 72.9 %. The melting point measurement
confirmed the purity of the product, demonstrating the efficiency of this reaction.

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