O
O
O
-
OCCH2CHCNHCHCOCH 3
+
NH3
CH–2 Química Orgânica II
Terceira lista de exercícios
Prof. Marco Antonio – 2015
aspartame
1) a) Qual das seguintes reações não fornecerá o produto carbonílico correspondente?
49. a. Which of the following reactions will not give the carbonyl product shown?
O
O
1. CH3COH + CH3CO
I17-669_730r3 28-03-2003
2:25 PM Page 725
O
O
3. CH3CNH2 + Cl
-
O
7. CH3CNHCH3 + CH3CO
O O
Problems
CH3COH
O O
O
10. CH3COCH3
CH3COH
725
O
9. CH3CNHCH3 + H2O
O
8. CH3CCl + H2O
CH3CCl
O
CH3COCCH3
O
O
6. CH3COCH3 + Cl-
BRUI17-669_730r3 28-03-2003 2:25 PM Page 726
-
CH3CNHCH3
O
CH3CCl
O
O
5. CH3COCH3 + CH3NH2
CH3COCCH3
O
CH3CNHCH3
O
O O
-
O
4. CH3COH + CH3NH2
CH3COCCH3
O
2. CH3CCl + CH3CO
O
O O
-
+
CH3OH
CH3COCH3
726
A PT
ER 1 7
Carbonyl
b.
WhichCH
of the
reactions
that do
not occurCompounds
can be made toI occur if an acid catalyst is added to the reaction mixture?
2) Dê o produto e forneça
o mecanismo
cada uma
reações:
50. 1,4-Diazabicyclo[2.2.2]octane
(abbreviated
DABCO) isde
a tertiary
aminedas
that catalyzes
transesterification reactions. Propose a
55.
Give
the
products
of
the
following
reactions:
mechanism to show how it does this.
O
O
N
a. CH3CCl + KF
N
O +
f.
1,4-diazabicyclo[2.2.2]octane
DABCO
excess
51. Identify theO
major and minor products of the following reaction:
NH + H O
2
b.
HCl
O
O
CH2OH
CH2CH3 + CH3CCl
O
CH3O-
g. CH3CCH2OCCH3 + CH3OH
excess
O
N
H
O
HCl
H2O
O
CH2COH
1. SOClfrom
3C)
2O
2
52. Two c.
products, A andCOH
B, are obtained
the reaction of 1-bromobutane with
with
acetyl
chloride to
h. NH 3 . Compound A reacts(CH
2. 2chloride
CH3NH2to form D. The IR spectra of C and D are shown. Identify A, B, C, and
D D.
form C, and B reacts with acetyl
2.5
2.6 2.7 2.8 2.9
3
3.5
4
4.5
5
5.5
6
7
8
9
10
COH11
12
13
14
15
16
O
O
i.
O + H2O
% Transmittance
d.
O
O +
NH3
excess
O
O
OH
Compound
C
O
O
OH
e. ClCCl +
4000
3800
3600
O
j.
3400
3200
3000
2800
2600
2400
2200
2000
1800
1600
1400
1200
2.6 2.7 2.8 2.9
3
3.5
4
4.5
5
5.5
6
800
O
Wavenumber (cm -1)
2.5
+
1000
7
8
9
10
11
12
HCl
CH3OH
600
excess
13
14
15
16
% Transmittance
56. When treated with an equivalent of methanol, compound A, with molecular formula C4H 6Cl 2O, forms the compound whose
1
H NMR spectrum is shown below. Identify compound A.
Compound D
4000
3800
3600
3400
3200
3000
2800
2600
2400
2200
2000
1800
1600
Wavenumber (cm -1)
1400
1200
1000
800
600
3) Explique a seguinte ordem de reatividade:
BRUI18-731_787r3 28-03-2003 1:33 PM Page 781
UI18-731_787r3 28-03-2003 1:33 PM Page 781
4) Forneça o produto e dê o mecanismo da seguinte reação:
47. Fill in the boxes:
a. CH3OH
1.
2.
CH3Br
781
CH3CHProblems
2OH
RUI18-731_787r3 28-03-2003 1:33 PM Page 781
47. 5)
FillDe
in the
boxes:
o produto
e o mecanismo de cada uma das reações:
a. CH3OH
b. CH4
b.1. CH4
CH3Br
2.
1.
2.
CH3CH2CH
OH3Br
CH3CH2CH2OH
48. Give the products of each of the following reactions:
1.
CH3CH2CH2OH
HCl
2.
C NCH2CH3 + H2O
a.
CH3Br
48.
47. Give
Fill inthe
theproducts
boxes: of each of the following reactions:
C NCH2CH3 + H2O
a.
CH3Br
a. CH3OH
CH2CH3
HCl
CH2CH3
O
1. LiAlH 4
O f.
CH3CH2OH
2. H O
O
1.N
CH3CH2MgBr 2
b. CH3CH2CCH3 2.HH O+
1.
2.
O
OCH CH CH OH
3
2
2
1.
2.
+ CH CH NH
g.
+ (C6H5)3P CHCH3 3 2 2
c.
48. Give the products of each of the following reactions:
O
O
HCl
O
catalytic
1. LiAlH4
1. CH3CH2MgBr
C NCH2CH3 + H2O
a.
f.
H+
excess2. H2O
O
+ (C6H5)3P CHCH3
c.
h. 3 N
+
d. CH3CH2COCH
+ (CH3CH2)2NH
CH2CH3
2.
H
O
H 3
i)
j)
O
e.
O
catalytic
H+
3
O
1. CH3CH2M gBr
O
excess
d. CH3CH2COCH3 1. 2.
CH3CH+2MgBr
b. CH3CH2CCH3 2. H HO3+O
3
k)
O
O
HCl
e.
+ CH3OH
+ (C6H5)3P CHCH3
c.
O CH3
+ CH3CH2NH2
g.
3
O
CH3Br
b. CH4
1. CH3CH2M gBr
b. CH3CH2CCH3 2. H O+
1. LiAlH4
f.Problems 781
2. H2O
O
N
H
+ (CH3CH2)2N
h.
CH3
i.
CH3C
O
CHCCH3 + H
O
HCl
CH3C
CHCCH
i.+ CH
3 + HBr
3OH + CH3CH2NH2
g.
catalytic
H+
O
j.
2 CH2
CH
COCH3
O of thiourea with an alkyl halide, followed by hydrox
49. Thiols can be prepared from
O the reaction
j. 2 CH2 CH SCOCH3 + catalytic
CH3+NH2
O
H
h.
+ (CH3CH2)2NH1. CH3CH2Br
C
C
+ CH3CH
H2N by hydroxide-ion-promoted
NH2 2. HO , H2O hydrolysis.
H2N
NH2
49. Thiols can be prepared from the reaction of thiourea with an alkyl halide, followed
ethanet
CH3 thiourea
O
O
urea
1. CH3CH2MgBr
S
O
excess
a.1. Propose
a mechanism
reaction.
C the
CHCCH
CH3CH2Br
d. CH3CH2COCH3 2. H O+
i. CH3for
3 + HBr
3
C
Cformed if the
+ alkyl
CH
-, H
3CH
2SH employed were pentyl bromide?
b.
What
thiol
would
be
halide
2.
HO
O
2
H2N
NH2
H2N
NH2
ethanethiol
O
thiourea 50. The only organic compound
urea obtained when compound Z undergoes the following sequence of
O
spectrum
shown.
Identify
compound Z.
HCl
a. Propose a mechanism for the reaction.
e.
j. 2 CH2 CH COCH3 + CH3NH2
+ CH3OH
1. phenylmagnesium bromide
MnO2
b. What thiol would be formed
if the alkyl halide employed were pentyl bromide?
Compound Z
2. H3O+
50. The only organic compound obtained when compound Z undergoes the following sequence of reactions gives the 1H NMR
49. Thiols can be prepared from the reaction of thiourea with an alkyl halide, followed by hydroxide-ion-promoted hydrolysis.
spectrum shown. Identify compound Z.
S
1. phenylmagnesium O
bromide
M nO
H2N
Compound Z 1. CH3CH+2Br
2. H3O
C
2. HO-, H2O
NH
thiourea
2
2
H2N
C
NH2
D CH SH
+ CH
3
2
ethanethiol
urea
Offset: 0.2 ppm.
a. Propose a mechanism for the reaction.
b. What thiol would be formed if the alkyl halide employed were pentyl bromide?
50. The only organic compound obtained when compound Z undergoes the following sequence of reactions gives the 1H NMR
D
owing compounds could be prepared,
usinghow
a Reformatsky
reaction: compounds could be prepared, using a Reformatsky reaction:
Describe
each of the following
O
O
CH3
CH3
OH
O
6) Quais reagentes são necessários
para a preparação de um álcool primário, a partir dos
CH
CH
CCOH
c.CHCH
3
2
a.
c. CH3CH2CH CCOH
CH
CH
CHCH
COCH
3 indicados?
2
2
2
3
materiais de partida
H3
OHOH O O
OH
b. d.CHCH
3CH
2CCH2COCH3
3CH
2CHCHCOH
O
d. CH3CH2CCH2COCH3
CH
CH22CH
CH33
CH2CH3
1 an acetoacetic ester synthesis. What alkyl
pectrum is shown here was obtained
the product
53. Theas
ketone
whose of
H NMR spectrum is shown here was obtained as the product of an acetoacetic ester synthesis. What alk
is?
halide was used in the synthesis?
7) Proponha uma rota sintética e forneça os mecanismos de cada etapa para a formação do
produto a seguir. Você pode utilizar mais de uma etapa.
7
6
5
4 10
3 9
(ppm)
você
prepararia os
frequency
2 8
1 7
06
8) Como
seguintes produtos a
mecanismo destas transformações:
5
4
3
2
(ppm)
partirfrequency
da ciclohexanona?
1
0
Forneça o
mpounds could be synthesized
cyclohexanone
and anycompounds
other necessary
54.from
Indicate
how the following
couldreagents:
be synthesized from cyclohexanone and any other necessary reagents:
O
c.
O
O
CH2CH2CCH3
a.
O
CH2CH2CH2CH3
e.
c)
O
O
O
O
O
O
O
CH
O
CH2CH2CCH3
c.
O
CH
e.
d)
O
O
COCH2CH3
CCH2CH2CH3 O
O
COCH2CH3
d.9) Explique a b.
f.
(tw o w ays)
d.
preparação dos seguintes compostos
a partir do mecanismo dasf.reações:
1
formula C6H 10 has two peaks55.
in its
H NMRAspectrum,
both offormula
which are
(with
ratioin9its
: 11).H NMR spectrum, both of which are singlets (with ratio
Compound
with molecular
C6Hsinglets
peaks
10 has two
cidic aqueous solution containingCompound
mercuric sulfate
to with
forman
compound
B thatsolution
gives a positive
A reacts
acidic aqueous
containing mercuric sulfate to form compound B that gives a positive
1
nd that has an 1H NMR spectrumiodoform
that shows
singlets
(with
: 1).anIdentify
A and
B. that shows two singlets (with ratio 3 : 1). Identify A and B.
testtwo
(Section
19.4)
andratio
that3has
H NMR
spectrum
a)
b)
10) Forneça as condições reacionais necessárias para obtenção dos seguintes produtos onde a
primeira etapa deve ser uma reação aldólica.
11) Partindo dos reagentes abaixo, escolha as condições reacionais adequadas para obtenção dos seguintes
produtos:
12) Forneça os mecanismos de oxidação da ciclohexanona utilizando PCC e Swern. Discuta as
vantagens e desvantagens de cada uma destas condições.