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CH312
Second semester Organic Chemistry
70
Chemistry
Undergraduate 2
12/27/2012

Additional Chemistry Flashcards

 


 

Cards

Term
 What is the structure of a peracid?
Definition
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Term

What is the reaction product of cyclohexene with MCBPA (m-chloroperbenzoic acid)?

 

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Definition
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Term
What is the product of the reaction of trans-2-butene with MCPBA?
Definition

Epoxidation reactions are stereospecific; a trans double bond will give the trans epoxide; cis double bonds will give the cis epoxide.

 

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Term

The following reaction is an example of a/an ________________   reaction.

 

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Definition
This is a reduction reaction and is accomplished by treating a ketone or aldehyde with NaBH4/CH3OH or LiAlH4 followed by H2O.
Term

What is the product of this reaction?

 

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Definition
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Term
Which reducing reagent is stronger, NaBH4/CH3OH or LiAlH4 followed by water?
Definition
LiAlH4 followed by water is a stronger reducing agent. It will reduce aldehydes, ketones, acid chlorides, acids, amides and esters to the corresponding alcohols. If you want to stop at an intermediate state (i.e. the aldehyde), you need a milder reducing agent.
Term

If you have an a,b unsaturated ketone, which reagent, below will reduce only the ketone and leave the double bond alone?

 

H2/Pd on C

NaBH4/CH3OH

 

Definition

NaBH4/CH3OH will only reduce the carbonyl and will leave the double bond alone.

 

 

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Term

If you have an a,b unsaturated ketone, which reagent, below will reduce only the double bond and leave the ketone alone?

 

H2/Pd on C (1 equivalent)

NaBH4/CH3OH

Definition

H2/Pd on C (1 equivalent) will reduce the double bond first.

 

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Term

If you want to make a saturated alcohol from an a,b unsaturated ketone, what reagent would you need?

 

H2/Pd on C (1 equivalent)

H2/Pd on C (excess)

NaBH4/CH3OH

Definition

H2/Pd on C (excess) will reduce the double bond first, and if you have enough, will reduce the ketone to an alcohol. 

NaBH4/CH3OH will not reduce the double bond no matter how much you have. H- is a nucleophile and won't attack the double bond because it has high electron density.

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Term

What is the product?

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Definition

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Amides may be synthesized from carboxylic acids provided that you include a "dehydrating agent" such as DCC (dicyclohexylcarbodiimide).

Term

LiAlH4 is a strong reducing agent. What are possible starting materials that would be suitable for the following reaction?

 

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Definition

There are quite a few suitable starting materials since LAH is such a strong reducing agent. Benzaldehye as well as the following compounds would work.

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Term

LiAlH4-type reducing agents have been modified to reduce the strength of this reagent. DIBAL-H is one example. What is the product of the following reduction reaction?

 

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Definition
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Term

Common, strong oxidizing agents such as K2Cr2O7 (potassium chromate) will take alcohols to acids. What is the starting material needed for the following reaction?

 

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Definition
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Term

What is the starting material?

 

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Definition

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Acids + amines + DCC --> amides

Term

What is the thermodynamically most stable enol form of this ketone?

 

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Definition

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           Thermodynamic enol              kinetic enol

 

The more substituted double bond is the most stable. The kinetic enol is formed first, and at low temperatures. 

Term

Name this ester

 

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Definition

four carbon acid - butyric acid or butanoic acid

four carbon alcohol - butanol (butyl alcohol)

 

butyl butyrate (common) or butyl butanoate (IUPAC)

Term

Name this ester

 

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Definition
Methyl 2,4-dimethylpentanoate
Term

What is the product?

 

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Definition

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The product is a mixed anhydride.

Term

What is the product?

 

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Definition

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The kinetic enolate (less substituted double bond) is formed under these reaction conditions, so alkylation takes place on the least substituted carbon.

Term

What is the product?

 

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Definition

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Formation of the thermodynamic enolate occurs under these reaction conditions (room temp, polar protic solvent). 

Term

Will the following reaction occur?

 

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Definition

 

Yes - esters can be hydrolyzed under basic or acidic conditions.

Term
What is the structure of octyl benzoate?
Definition
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Term

What functional group is present in this molecule?

 

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Definition
Cyclic esters are called lactones.
Term

Which of the following cannot be used to synthesize an ester?

 

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Definition

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Amides may not be used to sythesize esters; all others (acids, acid chlorides, anhydrides) may. 

Term

Name this compound:

 

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Definition
N-butyl-N-methyl-hexanamide
Term

What is the product?

 

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Definition
No reaction. Acids plus SOCl2 yield acid chlorides; esters are inert.
Term

What is the product?

 

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Definition
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Term

What is the reagent needed for the following reaction?

 

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Definition
propanol (CH3CH2CH2OH)
Term
Draw the structure of isopropyl formate
Definition

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Note: formic acid is HCO2H

Term

What are the starting materials needed to make this compound?

 

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Definition
Cyclopentanol and pentanoic acid (plus a little sulfuric acid as catalyst)
Term

Name this compound:

 

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Definition
2-methylheptanoyl chloride
Term
Draw the structure of methyl hexyl anhydride.
Definition
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Term

What are the products?

 

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Definition
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Term

How many alpha protons are in this molecule?

 

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Definition

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Four - three to the right of the carbonyl carbon and one to the left.

Term

What would the NMR spectrum of this ketone look like?

 

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Definition
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Term
Where is the C=O stretch (IR) for an ester?
Definition
1750 - 1700 cm-1
Term
How could you tell the difference between an ester and a carboxylic acid, using IR?
Definition

They would both have a carbonyl stretch around 1700

cm-1, but the carboxylic acid would also have a large, broad OH stretch around 3500 cm-1.

Term

What is the product of the following reaction?

 

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Definition
The corresponding carboxylic acid. Esters may be hydrolyzed to their corresponding acids with either base or acid.
Term

What is the starting material?

 

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Definition

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Anhydrides may be prepared by heating the heck out of acids if the acids are in close proximity.

Term

Which compound has the more acidic protons?

 

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Definition

Compound B (1,3-diketone) has the most acidic protons because the enolate is stabilized by several resonance forms.

 

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Term

Which carboxylic acid derivative has the highest reactivity?

 

Amide

Ester

Carboxylic acid

Acid Chloride

Anhydride

Definition

The order of reactivity is:

 

Acid Chlorides > Anhydrides > Esters, acids > Amides

Term

Name this compound:

 

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Definition

This is an acid chloride so the suffix is "oyl chloride". It is a derivative of benzoic acid, so you drop  the "ic acid" and replace it with the appropriate suffix.

 

Benzoyl chloride

Term

Which of the following compounds is more reactive towards nucleophilic attack?

 

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Definition
The lactam on the right is more reactive because it is a beta-lactam (four membered ring). The ring is strained, and it can relieve the strain by popping open, which is what happens when a nucleophile attacks the carbonyl carbon. This reactivity is the basis for the medicinal activity of beta-lactam antibiotics such as penicillin.
Term

What is the reagent needed to make an acid chloride from a carboxylic acid?

 

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Definition
Thionyl chloride (SOCl2)
Term

What reagents are needed to make the following compound from benzene?

 

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Definition

Friedel-Crafts acylation reactions require an acid chloride and AlCl3 catalyst.

 

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Term

What are the reagents needed for the following reaction?

 

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Definition

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This is a Friedel-Crafts alkylation and requires a haloalkane and aluminum chloride catalyst. This reaction works best if the carbocation that would result from the alkyl halide cannot rearrange - a simple alkyl halide like that above, or a tertiary alkyl halide. 

Term

What are the products of the following reaction?

 

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Definition

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Nitration of an aromatic ring is an electrophilic aromatic substitution reaction. Chloro and methy substituents are both ortho,para-directors, so the nitro group goes ortho and para to both groups. The isomer with the nitro group between the groups (ortho to both) will not form because of steric hindrance in a 1,2,3-trisubstituted benzene. 

Term

Is this compound aromatic?

 

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Definition

Yes, it is planar, cyclic, fully conjugated and satisfies Huckel's rule (4n + 2 electrons, where n = 0).

 

Term

Is pyrolle aromatic?

 

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Definition
Yes, it is planar, cyclic, fully conjugated and satisfies Huckel's rule (4n + 2 electrons, with n = 1). The six pi electrons of the aromatic system come from the double bonds (2x2 = 4) and the lone pair on nitrogen (2).
Term

Explain why pyridine is a good base, but pyrolle is not.

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pyridine   pyrolle   

Definition

Both compounds are aromatic, but the lone pair on nitrogen has a different role in each. In pyridine, the lone pair is orthogonal to the aromatic system and doesn't participate in the pi system. It is available for bonding. In pyrolle, the lone pair is part of the aromatic system. If it were to bond to a proton, that would disrupt the aromatic system.

 

 

Term

Label the following compounds as aromatic, antiaromatic or non-aromatic.

 

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Definition
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Term
What is the last step in electrophilic aromatic substitution?
Definition
Loss of a proton to reform the aromatic ring.
Term

Which of the following compounds will react fastest in electrophilic aromatic substitution reactions?

 

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Definition
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Term

What are the four criteria that must be met for a compound to be considered aromatic?

 

Definition

1) planar

2) fully conjugated

3) cyclic

4) 4n+2 electrons (Huckel's Rule)

Term

What is the product?

 

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Definition

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intramolecular Friedel Crafts acylation reaction

Term

Explain the following reaction:

 

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Definition

Friedel-Crafts reactions go through a carbocation-like intermediate which will rearrange to give the most stable carbocations.

Stability:  Primary < secondary < tertiary

Term

Which of the following compounds are meta directors in electrophilic aromatic substitution reactions?

 

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Definition
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Term
Which substituents on a benzene ring direct ortho-para with activation?
Definition
Groups that are electron donating such as alkyl groups, and functional groups such as -OH and -NH2 that have lone pairs on the heteroatom that is directly bonded to the benzene ring.
Term
Which substituents on a benzene ring direct ortho, para with deactivation?
Definition
Those electon-loving halogens: F, Cl, Br, I
Term
Which substituents on a benzene ring are meta directors, with deactivation.
Definition

All meta directors are deactivating. They are substituents that have a partially positive atom bonded to the aromatic ring. All substituents with a carbonyl group (aldehydes, ketones, carboxylic acids), -NO2, -SO3H, -CN, are meta directors.

Term
What reagent is needed to transform a carboxylic acid into an acid chloride?
Definition
SOCl2
Term

Which is faster?

 

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Definition
Reaction 2 is faster because the methoxy group donates electron density into the aromatic ring and thus is activating. It also directs ortho-para.
Term

What is the product of this reaction?

 

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Definition

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A Grignard reagent will add twice to an acid chloride or an ester. The first step is a substutiton reaction that gives a ketone as a product; the next step is the reaction of that ketone with another Grignard reagent to give an addition product.

Term

What is the product?

 

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Definition

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Grignard reagents and organolithium reagents will add 1,2 to an a,b-unsaturated carbonyl (they add to the ketone). 

Term

What is the product?

 

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Definition

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An organocopper reagent will add 1,4 to an a,b-unsaturated carbonyl compound.

Term

What is the reagent?

 

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Definition

 This is an addition reaction - a new carbon-carbon bond is formed at the carbonyl, turning it into an alcohol and a new 2-carbon fragment is added. Grignard or organolithium reagents will do this, so the reagent can be either CH3CH2MgBr or CH3CH2Li

Term

What is the product?

 

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Definition

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LiAlH4 (LAH) is a very strong reducing agent and will take ketones to alcohols, aldehydes to alcohols and amides to amines.

Term

What is the product?

 

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Definition

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NaBH4 (sodium borohydride) is a mild reducing agent and will reduce ketones and aldehydes to alcohols but not esters or acid chlorides.

Term
What effects determine if a substituted benzene reacts faster or slower than benzene in electrophilic aromatic substitution reactions?
Definition
Both inductive and resonance effects are important. Inductive effects are the "pull" that substituents have due to differences in electronegativity, and resonance effects either push electron density onto the ortho or para positions (through resonance structures) or pull it away.
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