Part 6

Question 1

Reductive amination

Answer 1

Process whereby an aldehyde or ketone is reacted with ammonia, a primary amine, or a secondary amine to form a primary, secondary, or tertiary amine, respectively.

Question 2

Amine + (Aldehyde or Ketone) –>

Answer 2

Product: Imine

Additional reduction with hydrogen in presence of a catalyst (Raney Nickel) = amine.

Question 3

Imine + (H2/Nickel) –>

Answer 3

Product: Amine

Question 4

Imine

Answer 4

Nitrogen double bonded to a carbon and has about the same polarity as a carbonyl functionality.

Question 5

DMSO

Answer 5

Good Polar Aprotic Solvent.

Therefore, good in SN2 reactions.

Question 6

CN-

Answer 6

Strong nucleophile.

Good in SN2 reactions.

Question 7

I-

Answer 7

Weak base, therefore good leaving group for SN2 reaction.

Question 8

Definition of aromtaticity

Answer 8

(4n + 2) pi

So, can be 2, 6, 10, etc…

Question 9

Cl2 + FeCl3 + Aromatic –>

Answer 9

Cl is Ortho, Para-directing, so will attach Cl to para or ortho positions depending on substituents.

Question 10

KMnO4

Answer 10

Oxidizing agent

Change toluene to COOH.

Question 11

HNO3/H2SO4 + toluene –> ?

Answer 11

R-groups are Ortho-, para- directing, so nitro will add to ortho or para position.

Question 12

Wolff-Kishner Reduction

Answer 12

Aldehydes and ketones can be completely reduced to alkanes by this metho. The carbonyl is first converted to a hydrazone, which releases molecular nitrogen when heated and forms an alkane. Only useful under basic conditions.

(use H2NNH2/Base/heat)

Question 13

Clemmensem Reduction

Answer 13

Where an aldehyde or ketone is heated with amalgamated zinc in hydrochloric acid.

Question 14

Grignard Addition

Answer 14

Grignard reagents (RMgX) add to the carbonyl groups of ESTERS to form KETONES; however, the ketones are more reactive than the initial esters and are readily attacked with more grignard reagent to make TERTIARY ALCOHOLS.

Question 15

Claisen Condensation

Answer 15

Important reaction of ESTERS.

Simplest case: two moles of ethyl acentate react under basic conditions to produce a beta-keto ester. Also called teh acetoacetic ester condensation.

Enolate ion of one ester acts as a nucleophile, attacking another ester.

Question 16

Grignard reagent

Answer 16

RMgX (equivalent to R- nucleophile)

Question 17

Transesterification

Answer 17

When a different alcohol attacks the ester, the ester is TRANSformed, and TRANSesterification results.

(ester into another ester)

Question 18

NH3 + ester –> ?

Answer 18

Answer: amide + alcohol

Nitrogen bases such as ammonia will attack the electron-deficient carbon atom, displacing alkoxide, to yield an amide and an alcohol side product.

Question 19

Hofmann Rearrangement

Answer 19

Converts amides to primary amines with the LOSS of the carbonyl carbon.

Involves the formation of a nitrene (nitrogen analog of carbene).

Question 20

Reduction of Amides –> ?

Answer 20

Amides can be reduced with LAH to the corresponding AMINE, but NO carbon is lost.

Question 21

KMnO4 + H2O2/OH-

Answer 21

Oxidation reagent. Will reduce to carboxylic acids.