Clutch Ch. 24. Amines And Heterocycles

Front 1

[H]

Back 1

LiAlH4

H2, Pd-C

Fe, HCl

Front 2

Amide reduced to primary amine

Back 2

[H]

Front 3

Nitrile reduced to primary amine

Back 3

[H] x 2

Front 4

NItro reduced to primary amine

Back 4

-[H], or

Chemoselective - SnCl2, H2O (Stannous Chloride; Tin II Chloride

Front 5

Azide

Back 5

N3; N=N+=N-

Front 6

Azide to primary amine

Back 6

Ph3P, H2O; (Triphenylphosphate and H2O; Wittig reaction)

Front 7

Reductive amination

Back 7

NH3, H+/NaBH3 CN

Front 8

Carbonyl to primary amine

Back 8

Reductive amination

Front 9

Curtius rearrangement

Back 9

Heat, H2O

Front 10

Acyl azide to primary amine

Back 10

The Curtius Rearrangement

Front 11

3 strong nitrogenous nucleophiles in SN2 reactions used in amines by reduction

Back 11

CN-

NO2-

N3-

Front 12

C=N + [H]

Back 12

NH2

Front 13

NO2- + [H] or SnCl2, H2O

Back 13

NH2

Front 14

N3- + Ph3P, H2O

Back 14

NH2

Front 15

Reductive amination step 1

Back 15

make the imine with NH3, H+ = (NH2+)

Front 16

Reductive animation step 2

Back 16

reduce the imine (NH2+) with NaBH3CN = (NH2)

Front 17

Gabriel synthesis

Back 17

An efficient way to make primary amines

Front 18

Gabriel synthesis step 1

Back 18

KOH is sused to turn phthalimide into a strong nucleophile

Front 19

Gabriel synthesis step 2

Back 19

Nucleophilic phthalimide does an SN2 attack on primary alkyl halide

Front 20

Gabriel synthesis step 3

Back 20

NH2-NH2 (hydrazine) attacks the carbonyls twice in a NAS attack.

Front 21

Gabriel synthesis 3 part step 3

Back 21

1. Remember the proton transfer to the new N-R group before the O- kicks the electrons down.

2. When the O- kicks down the electrons, the new N-R group gets kicked out and only has one bond to phthalimide.

3. Do the second carbonyl attack and remember steps 1 and 2)

Front 22

Reduction of acyl azides (N=N+=N-) is done how?

Back 22

The Curtius rearrangement; Heat and H2O

Front 23

Curtius rearrangement step1

Back 23

Heat; decompose N=N=+N- to a Nitrene and N gas (:N=N:)

Front 24

Curtius rearrangement step 2

Back 24

Nitrene does its rearrangement and you get isocyanate (O=N=C-R)

Front 25

Curtius rearrangement step 3

Back 25

H2O attacks isocyanate and you get carbamic acid.

(remember N- grabs an H from H2O after the acid is made because it has a negative charge)

Front 26

Curtius rearrangement step 4

Back 26

Decarboxylation (CO2 gas released) N grabs the H from O, you get a double bond between C and O, NH-R gets kicked out.

Front 27

Hofmann rearrangement (Hofmann degradation)

Back 27

Turns amides into primary amines

1. Amide rearranges into isocyanate

2. CO2 gas by-product

Front 28

Hofmann rearrangement 6 steps

Back 28

1. OH- attacks H on N, e- kicked up to O

2. double bond N attacks Br

3.OH- attacks H on N, e- kicked up to O

4. O kicks down e-, then rearrangement.

5. Isocyanate attacked by OH-

6. Decarboxylation; primary amine and CO2

Front 29

Hofmann elimination

Back 29

Double bond minor product on least substituted alkene.

Front 30

Hofmann elimination 3 steps

Back 30

1. CH3-I attacks NH2 x3 = N+(CH3)3

2. Ag2O, H2O, heat = AgO + OH-

3. OH- attacks least substituted beta H; minor product double bond

Front 31

Aniline reacts with nitrous acid (HNO2 or NaNO2) to produce

Back 31

Diazo functional group; (benzene) C6H5 N+=N

Front 32

C6H5 N+=N + CuBr, CuCl, CuCN

Back 32

C6H5 Br; bromobenzene

C6H5 Cl; bromochlorine

C6H5 CN; benzonitrile

Front 33

C6H5 N+=N + KI

C6H5 N+=N + HBF4

Back 33

C6H5 I; iodobenzene

C6H5 F; fluorobenzene

Front 34

C6H5 N+=N + H2O

C6H5 N+=N + H3PO2

Back 34

C6H5 OH; phenol

C6H5; benzene

Front 35

C6H5 N+=N + C6H5 EDG

Back 35

C6H5 N=N C6H5 EDG; Azo dye coupling reaction