Cuaderno Trabajo - 2019-1

1
CURSO DE VERANO QUÍMICA ORGÁNICA I

2019-1
UNIDAD DE INSTRUCCIÓN NO 03
1. Give two names for each of the following compounds:
Análisis 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?
1
por Jorge Luis Breña Oré : jbrenaore@yahoo.com
2
2019-1
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
2
3
2019-1
(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.
3
4
2019-1
(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.
4
5
2019-1
(a) Is a methyl group at C-6 that is “down” axial or equatorial?
(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.
5
6
2019-1
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
6
7
2019-1
20. One of the staggered conformations of 2-methylbutane in Problem 3.18b is more stable
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.
7
8
2019-1
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
8
9
2019-1
26. The potential energy diagram versus rotation angle for n-butane 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.
9
10
2019-1
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:
10
11
2019-1
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
11
12
2019-1
direction. Find the value of 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.
12
13
2019-1
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
13
14
2019-1
REACTIONS OF ALKANES
14
15
2019-1
31. Give the structure of the principal organic product formed by free-radical bromination of
each of the following:(a) Methylcyclopentane (b)1-Isopropyl-1-methylcyclopentane
(c) 2,2,4-Trimethylpentane Propose the reaction mechanism for the main product of the
reaction.
32. Use bond-dissociation enthalpies (Table 4-2) to calculate values of Ho for the following
reactions.
33. Use the information in Table 4-2) to rank the following radicals in decreasing order of
stability.
34. For each alkane,
1. Draw all the possible monochlorinated derivatives.
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?)
3. Which monobrominated derivatives could you form in good yield by free-radical bromination?
(a) cyclopentane (b) methylcyclopentane
(c) 2-methylpentane (d) 2,2,3,3-tetramethylbutane
15
16
2019-1
35. Write a mechanism for the light-initiated reaction of cyclohexane with chlorine to give
chlorocyclohexane. Label the initiation and propagation steps.
36. In the presence of a small amount of bromine, the following light-promoted reaction has
been observed
(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.)
(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.
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.
(a) cyclohexane (b) methylcyclopentane (c) isopentane (d) hexane.
38. When exactly 1 mole of methane is mixed with exactly 1 mole of chlorine and light is
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.
(a) Explain how a mixture is formed from this stoichiometric mixture of reactants, and propose
mechanisms for the formation of these compounds from chloromethane.
16
17
2019-1
(b) How would you run this reaction to conformacional
Análisis get a good conversion of methane
y reacciones to CHCl3. Of methane
de alcanos
to CCl4?
39. The chlorination of pentane gives a mixture of three monochlorinated products.
(a) Draw their structures.
(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.
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).
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.)
42. Tributyltin hydride (Bu3SnH) is used synthetically to reduce alkyl 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.
17
18
2019-1
The following bond-dissociation enthalpies may be helpful:
(a) Propose initiation and propagation steps to account for this reaction.
(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 materials by the Br .
Radicals. That should complete the initiation. Now decide what energetically favored
propagation steps will accomplish the reaction.
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:
18
19
2019-1
ESTEREOQUÍMICA
44. Assign absolute configurations as R or S to each of the following compounds:
45. Draw three-dimensional representations of (a) The R enantiomer of (b) The S enantiomer
of
46. 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?
19
20
2019-1
47. A second category of six-carbon carbohydrates, called ketohexoses, has the constitution
shown. How many stereoisomeric 2-ketohexoses are possible?
48. Which of the isomeric alcohols having the molecular formula C5H12O are chiral? Which
are achiral?
49. 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?
50. 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.
20
21
2019-1
51. 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?
52. In 1996, it was determined that the absolute configuration of

(-)-bromochlorofluoromethane is R. Which of the following is (are) (_)-BrClFCH?
53. Specify the configuration of the chirality center as R or S in each of the following.
(-)-2-Octanol
(b) Monosodium L-glutamate (only this stereoisomer is of any value as a flavor-enhancing agent)
54. 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.
21
22
2019-1
55. 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?
22
23
2019-1
23
24
2019-1
56. Chemical degradation of chlorophyll gives a number of substances including phytol. The
constitution of phytol is shown. How many stereoisomers have this constitution?
57. Muscarine is a poisonous substance present in the mushroom Amanita muscaria. Its
structure is represented by the constitution shown here.
58. Multifidene is a sperm cell-attracting substance released by the female of a species of

Brown algae (Cutleria multifida). The constitution of multifidene is
24
25
2019-1
(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)?
59. 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.
60. What are the pro-R and pro-S designations for the enantiotopic hydrogens in 1-propanol?
25

Cuaderno Trabajo - 2019-1

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Cuaderno Trabajo - 2019-1

Hochgeladen von

Copyright:

Verfügbare Formate

1

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

34. For each alkane,

1. Draw all the possible monochlorinated derivatives.

(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.

The following bond-dissociation energies may be helpful:

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

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

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

Das könnte Ihnen auch gefallen