Problem set

Here are the first questions of the Problem Set.

1) Predict the products from the reaction of toluene, nitrobenzene and m-chlorotoluene with:
a) 1-chloropropane/AlCl3
b) KMnO4 (hot, concentrated)
c) HNO3/H2SO4
d) HNO3/I2
e) AlI3/I2
f) t-butanol/BF3
g) SO3/H2SO4
h) Br2/light
i) PhCOCl/AlCl3
j) NaNH2
k) Br2/FeBr3
l) NaOH, 350C

2) Propose a synthesis of the following from benzene:
a) n-propylbenzene
b) m-chloronitrobenzene
c) p-iodoanisole
d) o-methylaniline
e) 1-bromo-1-phenylethane
f) methylcyclohexane

3) Predict the products from the reaction of benzaldehyde with:
a) Na2Cr2O7/H2SO4
b) KMnO4
c) PhMgBr then H3O+
d) CH3CH=PPh3
e) Ethylene glycol, H2SO4
f) HCN then H3O+,heat
g) NH2OH, H+
h) Acetone dimethyl ketal
i) NaBH4
j) NaBH3CN
k) NaBH3CN/isopropyl amine

4) Propose the synthesis of:
a) methyl ethyl ketone from 1,3-dithiane
b) benzaldehyde from toluene
c) acetophenone from ethynylbenzene
d) benzophenone from cyanobenzene
e) acetone from acetic acid
f) propionaldehyde from CH3CH2COCl
g) 2-hydroxybutanoic acid from propanoic acid

5) Predict the products from the reaction of 2-aminobutane with
a) methyl bromide (excess)
b) methyl bromide (excess) then Ag2O then heat
c) diethylamine/NaBH3CN
d) bromobenzene
e) benzoyl chloride then LiAlH4

6) Predict the products from the reaction of aniline with
a) NaNO2/HCl then H3O+
b) NaNO2/HCl then CuBr
c) NaNO2/HCl then CuCl
d) NaNO2/HCl then CuF
e) NaNO2/HCl then HBF4
f) NaNO2/HCl then H3PO2
g) Br2/FeBr3

7) Propose a synthesis of:
a) diethylmethylamine from ethylamine
b) phenylisopropylamine from benzene and acetone
c) meta-bromofluorobenzene from benzene
d) benzylamine from toluene
e) methylamine from CH3CONH2
f) 1-amino-2-phenylethane from benzylbromide
g) p-nitroaniline from aniline

8) Predict the products from the reaction of propanoic acid with:
a) LiAlH4
b) NaOH
c) acetyl chloride
d) CH3MgBr

9) Propose a synthesis of:
a) propanoic acid from 1-propanol
b) propanoic acid from ethanol
c) acetic acid from 2-pentyne
d) CH3NHCH2CH3 from acetic acid
e) CH3COOCH2CH3 from acetic acid
f) Acetic anhydride from ethanol
g) Acetophenone from an organocuprate

10) Draw the mechanisms for the formation of an amide from ammonia and CH3COOCH2CH3

11) Predict the products from the reaction of:
a) cyclohexanone with Br2(one equivalent)/CH3COOH
b) acetophenone with I2(excess)/NaOH
c) propanal with NaOH
d) 2-butanone with benzaldehyde(excess), H2SO4/heat
e) propanal with formaldehyde(excess), H2SO4/heat
f) 2,7-octanedione with NaOH/heat
g) 2,6-octanedione with H2SO4/heat
h) 2,5-octanedione with NaOH/heat
i) 2,4-octanedione with NaOH/heat
j) CH3CO2Et with NaOH
k) CH3CO2Et with NaOEt
l) CH3CO2Et with benzaldehyde(excess), NaOEt
m) CH3CO2Et with oxalic acid (HO2CCO2H) (excess), NaOEt
n) Diethyl malonate with 1) NaOEt 2) benzyl bromide 3) H3O+
o) Ethyl acetoacetate with 1) NaOEt 2) n-propyl bromide 3) H3O+
p) Cyclohexanone with 1) NaOH/methyl vinyl ketone/heat

12) Using an enolate reaction propose a synthesis of:
a) bromoacetone
b) methyl vinyl ketone
c) PhCH2CH2COCH3
d) PhCH2CH2COOH
e) PhCOCH2COOEt
f) PhCOCH2COPh
g) CH3CH(OH)CH2CHO
h) CHCl3