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Organic Chemistry Chapt 11
Reactions of Alkyl Halides Nucleophilic substitutions and eliminations
23
Chemistry
Undergraduate 2
11/21/2011

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Term

 

 

Alkyl Halides are electrophile or nucleophiles?

Definition

 

 

Electrophiles that involve polar reactions with nucleophiles and bases

Term

 

 

What is kinetics?

Definition
the relationship between the rate at which a reaction occurs and the concentration of reactancts
Term

 

 

What are second order reactions and what is the formula?

Definition

Reactions which the rate is linearly dependent on the concentrations of two species

 

=k x [RX] x [-OH]

 

k=rate constant

RX=CH3Br concentration in molarity

OH=OH concentration in molarity

Term

 

What does Sn2 reaction stand for?

 

Definition

 

 

*Short for Substitution, Nucleophilic, Bimolecular (2 molecules take place in the step where kinetics are measured [nucleophile and alkyl halide])

 

 

Term

 

 

How does Nucleophile attack substrate in Sn2 Reaction? What is the outcome?

Definition

*This takes place in a single step (no intermediate) 

*Nucleophile attacks from opposite side the halide is on (180 degrees)

*When Nucleophile electrons attaches is forces out the halide causing a transition state where the negative charge is delocalized

 [image]<--Transition state

 

*The back side approach causes the substrate to invert

(R would turn into an S vice versa)

 

 

Term

 

 

In Sn2 Reactions, do they work faster with more or less substrates attached to the carbon being attacked??

Definition

the less substrates the faster the reaction

 

***Vinylic and Aryl Halides CAN NOT react in Sn2 Reactions

Term
In Sn2 Reactions.....
A Negative nucleophile = a ______ Product 
Definition

 

 

Neutral Product

Term
In Sn2 Reactions...
A Nuetral nucleophile = a _______ product 
Definition

 

positive

Term
Nucleophilicity usually increases and you go _______  a column of the periodic table
Definition

 

 

 

DOWN

Term

 

 

Negative charged nucleophiles are more or less reactive than neutral ones?

Definition

 

 

MORE

Term
What does Sn1 reaction mean? What is its rate equation?
Definition

 

stands for subtitution nucleophile unimolecular

 

*It is a first order process which means the concentration of the nucleophole does not appear in the rate equation

=k x [RX]

Term

 

What is the highest transition state of energy in a Sn1 rxn called?

Definition

 

Rate limiting step or rate determining step

Term
How does an Sn1 reaction occur?
Definition
the leaving group leaves first, a carbocation intermediate is formed, the the nucleophile approaches leading to a racemic mixture of product enantiomers. 
Term

 

 

What does Benzylic mean?

Definition
means next to a aromatic ring
Term
Sn1 reactions prefer tertiary or secondary substrates?
Definition
 tertiary
Term

 

What solvents are preferred in Sn1 reactions?

Definition

 

polar protic solvents 

(alcohols, waters and so on)

 

*affects on rxn due to stabilization or destabilization of transtion state

Term

 

What happens during elimination reactions of alkyl halides?

Definition
Hydrogen halide is eliminated from alkyl halide to form an alkene
Term
What is Zaitevs rule?
Definition

According to Zaitsev’s rule, during elimination of HX from an alkyl halide, the more highly substituted alkene product predominates.

Term
E2 reactions are....
Definition

 stands for : elimination bimolecular

 

*alkyl halide treated with a STRONG base [-OH or RO-]

 

*there is no intermediate, acts like Sn2 and perfers antiperplanar  (all 4 reacting atoms lie in the same place but H and X are anti each other) 

*antiperplanar preferred because of Staggered realtion ship

Term

 

What is the rate equation of E2 reaction?

Definition

 

Rate= k [base][substrate]

Term
What is the E1 rxn and what the the rate formula
Definition

·        **Elimination of HX occurs by E1 mechanism if the alkyl halide is treated with a weak base or a non-basic nucleophile.

·      ***  An intermediate carbocation is generated in the process.
***rate  = k[substrate]

str

 

Term

 

What is E1cB rxn?

Definition

·        Takes place through a carbanion intermediate

·        Reaction common in substrates with poor leaving group, e.g. OH, two carbons away from a carbonyl group.

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