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35 Cards in this Set
- Front
- Back
[H] |
LiAlH4 H2, Pd-C Fe, HCl |
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Amide reduced to primary amine |
[H] |
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Nitrile reduced to primary amine |
[H] x 2 |
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NItro reduced to primary amine |
-[H], or Chemoselective - SnCl2, H2O (Stannous Chloride; Tin II Chloride |
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Azide |
N3; N=N+=N- |
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Azide to primary amine |
Ph3P, H2O; (Triphenylphosphate and H2O; Wittig reaction) |
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Reductive amination |
NH3, H+/NaBH3 CN |
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Carbonyl to primary amine |
Reductive amination |
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Curtius rearrangement |
Heat, H2O |
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Acyl azide to primary amine |
The Curtius Rearrangement |
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3 strong nitrogenous nucleophiles in SN2 reactions used in amines by reduction |
CN- NO2- N3- |
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C=N + [H]
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NH2
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NO2- + [H] or SnCl2, H2O
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NH2
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N3- + Ph3P, H2O
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NH2
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Reductive amination step 1 |
make the imine with NH3, H+ = (NH2+) |
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Reductive animation step 2 |
reduce the imine (NH2+) with NaBH3CN = (NH2) |
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Gabriel synthesis |
An efficient way to make primary amines |
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Gabriel synthesis step 1 |
KOH is sused to turn phthalimide into a strong nucleophile |
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Gabriel synthesis step 2 |
Nucleophilic phthalimide does an SN2 attack on primary alkyl halide |
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Gabriel synthesis step 3 |
NH2-NH2 (hydrazine) attacks the carbonyls twice in a NAS attack. |
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Gabriel synthesis 3 part step 3 |
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) |
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Reduction of acyl azides (N=N+=N-) is done how? |
The Curtius rearrangement; Heat and H2O |
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Curtius rearrangement step1 |
Heat; decompose N=N=+N- to a Nitrene and N gas (:N=N:) |
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Curtius rearrangement step 2
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Nitrene does its rearrangement and you get isocyanate (O=N=C-R) |
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Curtius rearrangement step 3
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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) |
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Curtius rearrangement step 4 |
Decarboxylation (CO2 gas released) N grabs the H from O, you get a double bond between C and O, NH-R gets kicked out. |
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Hofmann rearrangement (Hofmann degradation) |
Turns amides into primary amines 1. Amide rearranges into isocyanate 2. CO2 gas by-product |
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Hofmann rearrangement 6 steps |
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 |
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Hofmann elimination |
Double bond minor product on least substituted alkene. |
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Hofmann elimination 3 steps |
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 |
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Aniline reacts with nitrous acid (HNO2 or NaNO2) to produce |
Diazo functional group; (benzene) C6H5 N+=N |
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C6H5 N+=N + CuBr, CuCl, CuCN |
C6H5 Br; bromobenzene C6H5 Cl; bromochlorine C6H5 CN; benzonitrile |
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C6H5 N+=N + KI
C6H5 N+=N + HBF4 |
C6H5 I; iodobenzene
C6H5 F; fluorobenzene |
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C6H5 N+=N + H2O
C6H5 N+=N + H3PO2 |
C6H5 OH; phenol
C6H5; benzene |
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C6H5 N+=N + C6H5 EDG |
C6H5 N=N C6H5 EDG; Azo dye coupling reaction
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