Problemas

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CURSO DE VERANO QUÍMICA ORGÁNICA I

2019-1
UNIDAD DE INSTRUCCIÓN NO 03
1. Give two names for each of the following
Análisis compounds:
conformacional y reacciones de alcanos
2. Exclusive of compounds with double bonds, four hydrocarbons are constitutional

isomers of cis- and trans-1,2-dimethylcyclopropane. Identify these compounds.
3. certain hydrocarbon has a molecular formula of C5H8. Which of the following is not a
structural possibility for this hydrocarbon?
(a) It is a cycloalkane.
(b) It contains one ring and one double bond.
(c) It contains two double bonds and no rings.
(d) It is an alkyne.
4. Which of the hydrocarbons in each of the following groups are isomers?
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por Jorge Luis Breña Oré : jbrenaore@yahoo.com
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Análisis conformacional y reacciones de alcanos
5. Give the IUPAC name for each of the following compounds:
6. Draw the two chair conformers of each compound, and indicate which conformer is more
stable:
a. cis-1-ethyl-3-methylcyclohexane d. trans-1-ethyl-3-methylcyclohexane
b. trans-1-ethyl-2-isopropylcyclohexane e. cis-1-ethyl-3-isopropylcyclohexane
c. trans-1-ethyl-2-methylcyclohexane f. cis-1-ethyl-4-isopropylcyclohexane
7. Write a structural formula for each of the following compounds:
(a) 6-Isopropyl-2,3-dimethylnonane
(b) 4-tert-Butyl-3-methylheptane
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(c) 4-Isobutyl-1,1-dimethylcyclohexane
(d) sec-Butylcycloheptane
(e) Cyclobutylcyclopentane
8. The heats of combustion of methane and butane are 890 kJ/mol (212.8 kcal/mol) and
2876 kJ/mol (687.4 kcal/mol), respectively. When used as a fuel, would methane or
butane generate more heat for the same mass of gas? Which would generate more heat
for the same volume of gas?
9. In each of the following groups of compounds, identify the one with the largest heat of
combustion and the one with the smallest. (Try to do this problem without consulting
Table 2.3.)
(a) Hexane, heptane, octane
(b) 2-Methylpropane, pentane, 2-methylbutane
(c) 2-Methylbutane, 2-methylpentane, 2,2-dimethylpropane
(d) Pentane, 3-methylpentane, 3,3-dimethylpentane
(e) Ethylcyclopentane, ethylcyclohexane, ethylcycloheptane
10. The heats of combustion of ethylcyclopropane and methylcyclobutane have been
measured as 3352 and 3384 kJ/mol (801.2 and 808.8 kcal/mol). Assign the correct heat of
combustion to each isomer.
11. The reaction shown is important in the industrial preparation of dichlorodimethylsilane

for eventual conversion to silicone polymers.
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(a) Is carbon oxidized, reduced, or neither in this reaction?
(b) On the basis of the molecular model of (CH3)2SiCl2, deduce the hybridization state of
silicon in this compound. What is the principal quantum number n of the silicon s and p
orbitals that are hybridized?
12. Sketch a potential energy diagram for rotation around a carbon–carbon bond in propane.
Identify each potential energy maximum and minimum with a structural formula that
shows the conformation of propane at that point. Does your diagram more closely
resemble that of ethane or of butane? Would you expect the activation energy for bond
rotation in propane to be more than or less than that of ethane? Of butane?
13. Given the following partial structure, add a substituent X to C-1 so that it satisfies the
indicated stereochemical requirement.
14. The following questions relate to a cyclohexane ring depicted in the chair conformation
shown.
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C-6 that conformacional
(a) Is a methyl group at Análisis is “down” axial ory equatorial?
reacciones de alcanos
(b) Is a methyl group that is “up” at C-1 more or less stable than a methyl
group that is up at C-4?
(c) Place a methyl group at C-3 in its most stable orientation. Is it up or down?
15. Based on what you know about disubstituted cyclohexanes, which of the following two
stereoisomeric 1,3,5-trimethylcyclohexanes would you expect to be more stable?
16. Write structural formulas for the most stable conformation (representation of newman)
of each of the following compounds:
(a) trans-1-tert-Butyl-3-methylcyclohexane (b) cis-1-tert-Butyl-3-methylcyclohexane
(c) trans-1-tert-Butyl-4-methylcyclohexane (d) cis-1-tert-Butyl-4-methylcyclohexane
17. The two stereoisomeric bicyclo[4.4.0]decanes, called cis- and trans-decalin, are
important examples. Represents the Newman projection for each of the isomers.
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18. Give the IUPAC names of each of the following alkanes
19. Sight down the C-2—C-3 bond, and draw Newman projection formulas for the
(a) Most stable conformation of 2,2-dimethylbutane
(b) Two most stable conformations of 2-methylbutane
(c) Two most stable conformations of 2,3-dimethylbutane
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20. One of the staggered conformations of 2-methylbutane
Análisis conformacional in Problem
y reacciones 3.18b is more stable
de alcanos
tan the other. Which one is more stable? Why?
21. Sketch an approximate potential energy diagram for rotation about the carbon–carbon
bond in 2,2-dimethylpropane. Does the form of the potential energy curve of 2,2-
dimethylpropane more closely resemble that of ethane or that of butane?
22. Repeat the above problem for 2-methylbutane. It has to start from the least stable
conformation.
23. Identify all atoms that are (a) anti and (b) gauche to bromine in the conformation shown
for CH3CH2CH2Br.
24. Determine whether the two structures in each of the following pairs represent
constitutional isomers, different conformations of the same compound, or stereoisomers
that cannot be interconverted by rotation about single bonds.
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25. Represent the Newman projection for each of the following cycloalkanes.
H3C H3C
H H H H
CH3 CH3
H3C
H3C
H H H
H
CH3 CH3
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26. The potential energy diagram
Análisis versus rotation
conformacional angle forde
y reacciones n-butane
alcanos is proposed
below.
Ep
6,1 kcal
3,4 kcal
0,8 kcal
CH3 CH3 CH3 CH3

CH3
CH3
CH3 CH3
CH3
CH3
Ángulo de rotación
Estimate:
1. Energy cost for torsional + steric interactions: I CH3-H (equatorial)
2. Energy cost for torsional + steric interactions: I CH3- CH3 (equatorial)
3. Energy cost for steric interaction: I CH3- CH3 (gauche)
Data: Energy cost for the torsional interaction: I H- H = 0,9 kcal
Energy cost for steric interaction: I CH3- H (gauche) = 0,2 kcal
Consider any other interaction with an energy cost of 0 kcal.
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27. The diagram below shows the potential energy diagram versus the rotation angle of the
isopentane.
a) Complete the conformations involved in this diagram.
b) Determine the energy differences of the different conformations with respect to the more stable
confirmation.
Data: Energy costs:
I H-H (eclipsed) = 0.9 kcal / mol I CH3-CH3 (eclipsed) = 2.5 kcal / mol
I CH3-H (eclipsed) = 1.4 kcal / mol I CH3- CH3 (gauche) = 1 kcal / mol
I CH3- H (gauche) = 0 kcal / mol
= CH3
Legend:
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EP
Ángulo de rotación
28. Below is the diagram of potential energy versus rotation angle of isopentane,
around C2-C3. Complete Newman's representations of the other conformations,
considering that the rotation occurs in the carbon behind, in a counterclockwise
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direction. Find
Análisis the
conformacional value de alcanosof
y reacciones X.
Ep
2,7 kcal
X
Avance
Legend:  = CH3
DATE
Type of interaction Energy costs ( kcal / mol )
Torsional tension H-H eclipsed 0,9s

Esteric tension CH3- CH3 gauche 0,9
Torsional + steric tension CH3- CH3 eclipsed 2.5
Torsional + steric tensión CH3- H eclipsed 1.5
29. Draw a diagram of potential energy versus rotation angle for the compound
shown below, around C2-C3. He has to use trestle projections, start with a less
stable conformation and show the energy differences with respect to the less
stable conformation.
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Energy costs:
IMeMe(e)  12 kJ / mol IMe H (e)  06 kJ / mol

I H H (e)  4 kJ / mol IMeMe( g )  3,8 kJ / mol
30. Calculate the energy difference between the two chair conformations, for the
compound shown:
Cl
CH3
CH3
Energy costs:
Interactions kcal/mol Interactions kcal/mol

Diaxial interactions 1,3- CH3-H 0,9 interactions CH3-H gauche 0
interactions CH3-Cl gauche 0,65 interactions CH3- CH3 0,9

gauche
interactions H-Cl gauche 0 Diaxial interactions 1,3- Cl-H 0,6
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REACTIONS
Análisis OF ALKANES
conformacional y reacciones de alcanos
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31. Give the structure of the principal
Análisis organic
conformacional product de
y reacciones formed by free-radical
alcanos
bromination of each of the following:
Indique la estructura del principal producto orgánico formado por bromación de radicales
libres de cada uno de los siguientes:
(a) Methylcyclopentane
(b)1-Isopropyl-1-methylcyclopentane
(c) 2,2,4-Trimethylpentane
Propose the reaction mechanism for the main product of the reaction.
Proponer el mecanismo de reacción para el producto principal de la reacción.
32. Use bond-dissociation enthalpies (Table 4-2) to calculate values of Ho for the
following reactions.
Utilice entalpías de disociación de enlace (Tabla 4-2) para calcular los valores de Ho para
las siguientes reacciones.
33. Use the information in Table 4-2) to rank the following radicals in decreasing order
of stability.
Use la información en la Tabla 4-2) para clasificar los siguientes radicales en orden
decreciente de estabilidad.
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34. For each alkane, Análisis conformacional y reacciones de alcanos
Para cada alcano,
1. Draw all the possible monochlorinated derivatives.
Dibuje todos los posibles derivados monoclorados.
2. Determine whether free-radical chlorination would be a good way to make any of these
monochlorinated derivatives. (Will the reaction give mostly one major product?)
Determine si la cloración por radicales libres sería una buena manera de hacer cualquiera de estos
derivados monoclorados. (¿La reacción dará mayormente un producto principal?)
3. Which monobrominated derivatives could you form in good yield by free-radical

bromination?
¿Qué derivados monobromados podrían formarse con buen rendimiento por bromación
de radicales libres?
(a) cyclopentane (b) methylcyclopentane
(c) 2-methylpentane (d) 2,2,3,3-tetramethylbutane
35. Write a mechanism for the light-initiated reaction of cyclohexane with chlorine to give
chlorocyclohexane. Label the initiation and propagation steps.
Escribe un mecanismo para la reacción iniciada por la luz del ciclohexano con cloro para
dar clorociclohexano. Etiqueta los pasos de iniciación y propagación.
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36. In the presence of a small amount
Análisis of bromine, the
conformacional followingde
y reacciones light-promoted
alcanos reaction
has been observed
En presencia de una pequeña cantidad de bromo, se ha observado la siguiente reacción
promovida por la luz.
(a) Write a mechanism for this reaction. Your mechanism should explain how both
products are formed. (Hint: Notice which H atom has been lost in both products.)
Escribe un mecanismo para esta reacción. Su mecanismo debe explicar cómo se forman
ambos productos. (Sugerencia: observe qué átomo de H se ha perdido en ambos productos).
(b) Explain why only this one type of hydrogen atom has been replaced, in preference
to any of the other hydrogen atoms in the starting material.
Explique por qué solo este tipo de átomo de hidrógeno ha sido reemplazado, con
preferencia a cualquiera de los otros átomos de hidrógeno en el material de partida.
37. For each compound, predict the major product of free-radical bromination.
Remember that bromination is highly selective, and only the most stable radical will
be formed.
Para cada compuesto, predice el principal producto de la bromación de radicales libres.
Recuerde que la bromación es altamente selectiva, y solo se formará el radical más estable.
(a) cyclohexane (b) methylcyclopentane (c) isopentane (d) hexane.
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38. When exactly 1 mole of methane
Análisis is mixed with yexactly
conformacional 1 mole
reacciones deof chlorine and light is
alcanos
shone on the mixture, a chlorination reaction occurs. The products are found to
contain substantial amounts of di-, tri-, and tetrachloromethane, as well as unreacted
methane.
Cuando se mezcla exactamente 1 mol de metano con exactamente 1 mol de cloro y la luz
brilla sobre la mezcla, se produce una reacción de cloración. Se encuentra que los productos
contienen cantidades sustanciales de di-, tri- y tetraclorometano, así como metano sin
reaccionar.
(a) Explain how a mixture is formed from this stoichiometric mixture of reactants,
and propose mechanisms for the formation of these compounds from chloromethane.
Explique cómo se forma una mezcla a partir de esta mezcla estequiométrica de reactivos,
y proponga mecanismos para la formación de estos compuestos a partir de clorometano.
(b) How would you run this reaction to get a good conversion of methane to CHCl3. Of
methane to CCl4?
¿Cómo ejecutaría esta reacción para obtener una buena conversión de metano a CHCl3?
De metano a CCl4?
39. The chlorination of pentane gives a mixture of three monochlorinated products.

La cloración del pentano da una mezcla de tres productos monoclorados.
(a) Draw their structures.
Dibuja sus estructuras.
(b) Predict the ratios in which these monochlorination products will be formed,
remembering that a chlorine atom abstracts a secondary hydrogen about 4.5 times
as fast as it abstracts a primary hydrogen.
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Predice las proporciones en las que se formarán estos productos de monocloración,

recordando que un átomo de cloro extrae un hidrógeno secundario aproximadamente 4.5
veces más rápido que un hidrógeno primario.
40. Peroxides are often added to free-radical reactions as initiators because the oxygen–
oxygen bond cleaves homolytically rather easily. For example, the bond-dissociation
enthalpy of the O-O bond in hydrogen peroxide (HO - OH) is only 213 kJ mol (51 kcal
mol). Give a mechanism for the hydrogen peroxide-initiated reaction of cyclopentane
with chlorine. The Do for HO-Cl is 210 kJ mol (50 kcal/mol).
Los peróxidos se agregan a menudo a las reacciones de radicales libres como iniciadores
porque el enlace oxígeno-oxígeno se rompe de manera homolítica con bastante facilidad.
Por ejemplo, la entalpía de disociación de enlace del enlace O-O en el peróxido de
hidrógeno (HO-OH) es de solo 213 kJ mol (51 kcal mol). Dar un mecanismo para la
reacción iniciada por el peróxido de hidrógeno de ciclopentano con cloro. El Do para HO-
Cl es 210 kJ mol (50 kcal / mol).
41. When a small amount of iodine is added to a mixture of chlorine and methane, it
prevents chlorination from occurring.Therefore, iodine is a free-radical inhibitor for
this reaction. Calculate Ho values for the possible reactions of iodine with species
present in the chlorination of methane, and use these values to explain why iodine
inhibits the reaction. (The I-Cl bond-dissociation enthalpy is 211 kJ mol or 50 kcal
mol.)
Cuando se agrega una pequeña cantidad de yodo a una mezcla de cloro y metano, evita que
se produzca la cloración. Por lo tanto, el yodo es un inhibidor de radicales libres para esta
reacción. Calcule los valores de Ho para las posibles reacciones del yodo con especies
presentes en la cloración del metano, y use estos valores para explicar por qué el yodo
inhibe la reacción. (La entalpía de disociación del enlace I-Cl es 211 kJ mol o 50 kcal mol)
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42. Análisis
Tributyltin hydride (Bu 3SnH) conformacional y reacciones
is used synthetically to reducedealkyl
alcanos
halides, replacing
a halogen atom with hydrogen. Freeradical initiators promote this reaction, and free-
radical inhibitors are known to slow it or stop it. Your job is to develop a mechanism,
using the following reaction as the example.
El hidruro de tributilestaño (Bu3SnH) se usa sintéticamente para reducir los haluros de
alquilo, reemplazando un átomo de halógeno con hidrógeno. Los iniciadores freeradical
promueven esta reacción, y se sabe que los inhibidores de radicales libres la desaceleran o
la detienen. Tu trabajo es desarrollar un mecanismo, usando la siguiente reacción como
ejemplo.
The following bond-dissociation enthalpies may be helpful:
Las siguientes entalpías de disociación de enlace pueden ser útiles:
(a) Propose initiation and propagation steps to account for this reaction.
Proponer pasos de inicio y propagación para dar cuenta de esta reacción.
(b) Calculate Ho values of for your proposed steps to show that they are energetically
feasible. (Hint: A trace of Br2 and light suggests it’s there only as an initiator, to create Br .
Radicals. Then decide which atom can be abstracted mosr favorably from the starting
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.
Análisis conformacional
materials by the Br Radicals. y reacciones
That should complete de alcanos
the initiation. Now decide what
energetically favored propagation steps will accomplish the reaction.
Calcule Ho valores de para los pasos propuestos para demostrar que son energéticamente
viables. (Sugerencia: un rastro de Br2 y luz sugiere que está allí solo como un iniciador,
para crear Radicales. Luego, decida qué átomo se puede abstraer más favorablemente de
los materiales iniciales por parte de los Radicales. Eso debería completar la iniciación.
Ahora decida qué propagación favoreció energéticamente Los pasos lograrán la reacción.
43. Iodination of alkanes using iodine (I2) is usually an unfavorable reaction. (See Problem 4-
17, for example.) Tetraiodomethane (CI4) can be used as the iodine source for iodination,
in the presence of a free-radical initiator such as hydrogen peroxide. Propose a mechanism
(involving mildly exothermic propagation steps) for the following proposed reaction.
Calculate the value of Ho for each of the steps in your proposed mechanism.
The following bond-dissociation energies may be helpful:
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ESTEREOQUÍMICA
44. Assign absolute configurations as R or S to each of the following compounds:

Asigne configuraciones absolutas como R o S a cada uno de los siguientes compuestos:
45. Draw three-dimensional representations of (a) The R enantiomer of (b) The S enantiomer
of
46. Dibuje representaciones tridimensionales de (a) el enantiómero R de (b) el enantiómero S de
47. Biological reduction of pyruvic acid, catalyzed by the enzyme lactate dehydrogenase, gives
(-)-lactic acid, represented by the Fischer projection shown.
What is the configuration of (-)-lactic acid according to the Cahn–Ingold–Prelog R–S
notational system?
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48. A second category of six-carbon carbohydrates, called ketohexoses, has the constitution
shown. How many stereoisomeric 2-ketohexoses are possible?
49. Which of the isomeric alcohols having the molecular formula C5H12O are chiral? Which
are achiral?
50. Write structural formulas for all the compounds that are trichloro derivatives of
cyclopropane. (Don’t forget to include stereoisomers.) Which are chiral? Which are
achiral?
51. In each of the following pairs of compounds one is chiral and the other is achiral. Identify
each compound as chiral or achiral, as appropriate.
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52. Compare 2,3-pentanediol and 2,4-pentanediol with respect to the number of stereoisomers
possible for each constitution. Which stereoisomers are chiral? Which are achiral?
53. In 1996, it was determined that the absolute configuration of

(-)-bromochlorofluoromethane is R. Which of the following is (are) (_)-BrClFCH?
54. Specify the configuration of the chirality center as R or S in each of the following.
(-)-2-Octanol
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(b) Monosodium L-glutamate (only this stereoisomer is of any value as a flavor-enhancing agent)
55. A subrule of the Cahn–Ingold–Prelog system specifies that higher mass number takes
precedence over lower when distinguishing between isotopes.
(a) Determine the absolute configurations of the reactant and product in the biological
oxidation of isotopically labeled ethane.
56. Identify the relationship in each of the following pairs. Do the drawings represent
constitutional isomers or stereoisomers, or are they just different ways of drawing the same
compound? If they are stereoisomers, are they enantiomers or diastereomers?
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57. Chemical degradation of chlorophyll gives a number of substances including phytol. The
constitution of phytol is shown. How many stereoisomers have this constitution?
58. Muscarine is a poisonous substance present in the mushroom Amanita muscaria. Its
structure is represented by the constitution shown here.
59. Multifidene is a sperm cell-attracting substance released by the female of a species of

Brown algae (Cutleria multifida). The constitution of multifidene is
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(a) How many stereoisomers are represented by this constitution?

(b) Multifidene has a cis relationship between its alkenyl substituents. Given this information,
how many stereoisomers are possible?
(c) The butenyl side chain has the Z configuration of its double bond. On the basis of all the
data, how many stereoisomers are possible?
(d) Draw stereochemically accurate representations of all the stereoisomers that satisfy the
structural requirements of multifidene.
(e) How are these stereoisomeric multifidenes related (enantiomers or diastereomers)?
60. Streptimidone is an antibiotic and has the structure shown. How many diastereomers of
streptimidone are possible? How many enantiomers? Using the E–Z and R–S descriptors,
specify all essential elements of stereochemistry of streptimidone.
61. What are the pro-R and pro-S designations for the enantiotopic hydrogens in 1-propanol?
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CURSO DE VERANO QUÍMICA ORGÁNICA I

2. Exclusive of compounds with double bonds, four hydrocarbons are constitutional

(b) It contains one ring and one double bond.

(c) It contains two double bonds and no rings.

4. Which of the hydrocarbons in each of the following groups are isomers?

5. Give the IUPAC name for each of the following compounds:

7. Write a structural formula for each of the following compounds:

(a) Hexane, heptane, octane

(b) 2-Methylpropane, pentane, 2-methylbutane

(c) 2-Methylbutane, 2-methylpentane, 2,2-dimethylpropane

(d) Pentane, 3-methylpentane, 3,3-dimethylpentane

(e) Ethylcyclopentane, ethylcyclohexane, ethylcycloheptane

10. The heats of combustion of ethylcyclopropane and methylcyclobutane have been

11. The reaction shown is important in the industrial preparation of dichlorodimethylsilane

(a) Is carbon oxidized, reduced, or neither in this reaction?

group that is up at C-4?

(a) trans-1-tert-Butyl-3-methylcyclohexane (b) cis-1-tert-Butyl-3-methylcyclohexane

(c) trans-1-tert-Butyl-4-methylcyclohexane (d) cis-1-tert-Butyl-4-methylcyclohexane

18. Give the IUPAC names of each of the following alkanes

(a) Most stable conformation of 2,2-dimethylbutane

(b) Two most stable conformations of 2-methylbutane

(c) Two most stable conformations of 2,3-dimethylbutane

CH3 CH3 CH3 CH3

1. Energy cost for torsional + steric interactions: I CH3-H (equatorial)

2. Energy cost for torsional + steric interactions: I CH3- CH3 (equatorial)

3. Energy cost for steric interaction: I CH3- CH3 (gauche)

Data: Energy cost for the torsional interaction: I H- H = 0,9 kcal

Energy cost for steric interaction: I CH3- H (gauche) = 0,2 kcal

Consider any other interaction with an energy cost of 0 kcal.

Data: Energy costs:

I CH3- H (gauche) = 0 kcal / mol

Type of interaction Energy costs ( kcal / mol )

Torsional tension H-H eclipsed 0,9s

IMeMe(e)  12 kJ / mol IMe H (e)  06 kJ / mol

Interactions kcal/mol Interactions kcal/mol

interactions CH3-Cl gauche 0,65 interactions CH3- CH3 0,9

1. Draw all the possible monochlorinated derivatives.

Dibuje todos los posibles derivados monoclorados.

3. Which monobrominated derivatives could you form in good yield by free-radical

(a) cyclopentane (b) methylcyclopentane

(c) 2-methylpentane (d) 2,2,3,3-tetramethylbutane

39. The chlorination of pentane gives a mixture of three monochlorinated products.

(a) Draw their structures.

Dibuja sus estructuras.

Predice las proporciones en las que se formarán estos productos de monocloración,

The following bond-dissociation enthalpies may be helpful:

Las siguientes entalpías de disociación de enlace pueden ser útiles:

Proponer pasos de inicio y propagación para dar cuenta de esta reacción.

The following bond-dissociation energies may be helpful:

44. Assign absolute configurations as R or S to each of the following compounds:

53. In 1996, it was determined that the absolute configuration of

59. Multifidene is a sperm cell-attracting substance released by the female of a species of

(a) How many stereoisomers are represented by this constitution?

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