PROBLEMAS FIQT QUIMICA ORGÁNICA I 1 de

01 PROBLEMAS SOBRE CONOCIMIENTOS PREVIOS septiembre

GRUPOS FUNCIONALES -ISOMERIA de 2019

Primera semana de clase 26 de agosto al 31 de agosto 2019

RESUMEN DE LA INTENSIDAD DE LAS INTERACCIONES MOLECULARES

PROBLEMAS PARA LA PRACTICA 1

ESTRUCTURAS DE LEWIS

1. Write the structures of all isomers associated with the following global formulas:

1) C2H4O 2) C7H16 3) C5H10O (ketones) 4) C3H6ClBr2

5) C4H8 6) C3H9N 7) C4H10O 8) C5H10O(aldehídos)

9) C3H6O2 (It does not contain C = C links, or O-O links

10) C5H10 (todos los átomos de C con hibridación sp3)

1
 2. Which of the following pure compounds can form hydrogen bonds? Which can
form hydrogen bonds with water? Which ones do you expect to be soluble in water?

3. Many naturally occurring compounds contain more than one functional group. Identify
the functional groups in the following compounds and what is the molecular formula?:
(a) Penicillin G is a naturally occurring antibiotic.
(b) Dopamine is the neurotransmitter that is deficient in Parkinson’s disease.
(c) Capsaicin gives the fiery taste to chili peppers.
(d) Thyroxine is the principal thyroid hormone.
(e) Testosterone is a male sex hormone.

4. N-Methylpyrrolidine has a boiling point of 81 °C, and piperidine has a boiling point of 106
°C.
(a) Explain this large difference (25 °C) in boiling point for these two isomers.
(b) Tetrahydropyran has a boiling point of 88 °C, and cyclopentanol has a boiling point of 141 °C.
These two isomers
have a boiling point difference of 53 °C. Explain why the two oxygen-containing isomers have a
much larger boiling
point difference than the two amine isomers.
(c) N,N-Dimethylformamide has a boiling point of 150 °C, and N-methylacetamide has a boiling
point of 206 °C, for a difference of 56 °C. Explain why these two nitrogen-containing isomers
have a much larger boiling point difference than the two amine isomers. Also explain why these
two amides have higher boiling points than any of the other four compounds shown (two amines,
an ether, and an alcohol).

5. 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.
 6. Give the IUPAC names of each of the following alkanes

7. 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

SEGUNDA Y TERCERA SEMANA

8. 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. 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:
EP

Ángulo de rotación

10. 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 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

11. 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.

Energy costs:

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

mol
IMeMe(g)  3,8 kJ / mol
IH H (e)  4 kJ / mol

12. 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 gauche 0,9

interactions H-Cl gauche 0 Diaxial interactions 1,3- Cl-H 0,6

 REACTIONS OF ALKANES

13. 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.
 14. Use bond-dissociation enthalpies (Table 4-2) to calculate values of Ho for the following reactions.

15. Use the information in Table 4-2) to rank the following radicals in decreasing order of stability.

16. 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

17. Write a mechanism for the light-initiated reaction of cyclohexane with chlorine to give
chlorocyclohexane. Label the initiation and propagation steps.

18. 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.

19. 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.

20. 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.

(b) How would you run this reaction to get a good conversion of methane to CHCl 3. Of methane to CCl4?

21. 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.

22. 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 D o for HO-Cl is 210 kJ mol
(50 kcal/mol).

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.)

23. Escriba todos los isómeros de fórmula C4H8Br2

24. Determine si cada uno de los siguientes pares son isómeros estructurales, estereoisómeros
(diasterómeros, enantiómeros), meso, confórmeros o moléculas diferentes.

25. Se somete a monocloración el (S)-2-flúorbutano , obteniéndose todos los isómeros de fórmula

C4H8FCl. Determine

a. El nombre y formula estructural y/o estereoquímica, cuando corresponda para todos los isómeros
formados.

b. Si por destilación fraccionada cuidadosa se separan todos los compuestos formados, ¿cuántas
fracciones se destilan?

c.- ¿Cuántas fracciones se recuperan?, ¿cuántas fracciones presentan actividad óptica?,

d.- Rotule con números romanos a todos los compuestos formado, ¿Cuántos de los compuestos
formados presentan actividad óptica?

e. Identifique los pares de enantiómeros, diastereómeros y formas meso

 26. Resuelva el problema anterior para el (R)-2-clorobutano.
27. Se somete a monocloración el isopentano obteniéndose todos los isómeros de fórmula C5H9Cl.
Determine
a. El nombre y formula estructural y/o estereoquímica, cuando corresponda para todos los isómeros
formados.
b. Si por destilación fraccionada cuidadosa se separan todos los compuestos formados, ¿cuántas
fracciones se destilan?
c.- ¿Cuántas fracciones se recuperan?, ¿cuántas fracciones presentan actividad óptica?,
d.- Rotule con números romanos a todos los compuestos formado, ¿Cuántos de los compuestos
formados presentan actividad óptica?
e.- Identifique los pares de enantiómeros, diastereómeros, isómeros estructurales y formas meso.

28. Draw all possible stereoisomers for each of the following compounds. State if
no stereoisomers are possible.
a. 1-bromo-2-chlorocyclohexane g. 1,2-dimethylcyclopropane

b. 2-bromo-4-methylpentane h. 4-bromo-2-pentene

c. 1,2-dichlorocyclohexane i. 3,3-dimethylpentane

d. 2-bromo-4-chloropentane j. 3-chloro-1-butene

e. 3-heptene k. 1-bromo-2-chlorocyclobutane

f. 1-bromo-4-chlorocyclohexane l. 1-bromo-3-chlorocyclobutane

29. Indicate whether each of the following pairs of compounds are identical or are enantiomers,
diastereomers, or constitutional isomers:
29.Dar explicación completa sobre la diferencia de reactividad y selectividad de la cloración y
bromacion del propano. (justificar con fenómenos energéticos, velocidad y estabilidad de
especies químicas)
30.Para el ciclohexano disustituido (dimetil) 1,3-cis, es más estable que su isómero trans ; pero para
el caso del dimetil 1,2, ocurre lo contrario. Dar explicación.
31.Establecer la relación estereoisomerica de las estructuras (a) con (b), (a) con (c) y (b) con (d).

CH3
H3C

CH3
CH3

CH3

CH3

32.Para la reacción general

R-X + Nu → R-Nu + X-
Ordenar de menor a mayor (según velocidad de reacción r ) si la reacción se da en igualdad de
condiciones (concentración, temperatura, etc.) para los siguientes casos:

Para diferentes sustratos:

Cloruro de etilo (r1), yoduro de etilo (r2), fluoruro de etilo (r3) .

Con diferentes nucleofilos

OH- (r1), agua (r2), metanol (r3) .

Con diferentes sustratos

Cloruro de isopropilo (r1), cloruro de metilo (r2), cloruro de neopentilo (r3) . (3 Ptos)

33.If you understand the factors and principles that influence the course of nucleophilic substitution
reactions, try your hand at the following exercises. For each case the possibility of a substitution
versus no reaction must be considered. If a substitution is predicted will it take place by a S N1 or a
SN2 mechanism? If chiral centers are present will the configuration change?
34.Ordenar los compuestos de cada conjunto de acuerdo con su reactividad en el mecanismo Sn2
y luego Sn1.
a. 2-bromo-2-metilbutano, 1-bromopentano, 2-brompentano.
b. 1-bromo-3-metilbutano, 2-bromo-2-metilbutano, 2-bromo-3-metilbutano
c. 1-bromobutano, 1-bromo-2,2-dimetilpropano, 1-bromo-2-metilbutano, 1-bromo-3-
metilbutano.

35.Complete el esquema y los mecansimos de reacción para cada uno de los casos
36.¿Cuál de los siguientes haluros de alquilo forma un producto de sustitución en una reacción SN1
que sea distinto del producto de sustitución formado en una reacción SN2? Proponga el
mecanismo de reacción para ese producto.

37.edecir los productos de sustitución que se forman en las siguientes reacciones:

a) (R)-2-Clorobutano + etóxido sódico en etanol
b) (R)-2-Clorobutano + óxido de plata húmedo
c) (R)-2-Cloro-2-fenilbutano + cianuro potásico en agua.

38.Problema 15 página 218. Libro Química Orgánica Morrison.

39.Proporcione la configuración del producto de sustitución que se obtendrá a

partir de la reacción de los siguientes halogenuros de alquilo con el nucleófilo
indicado:
 40.Considerando eliminación E2 con etóxido de sodio en etanol. ¿cuál de los estereoisómeros del 3-
bromo-2, 3, 4-trimetilhexano produce el (Z)-2,3,4-trimetil-3-hexeno?

CH3
CH3 CH CH3

C
CH3 CH3
C CH2
41.La solvólisis de (2R, 3R)-2-bromo-3-metilpentano produce dos isómeros de fórmula
global C6H14O, A ( inactivo ) y B (ópticamente activo)

H2O
(2R,3R)-2-Bromo-3-metilpentano A +B
Reflujo
Determine el mecanismo de reacción para el producto B (ópticamente activo) mostrando la
estereoquímica de la reacción.

ii.- Escriba fórmulas estructurales o proyecciones de Fischer con sus respectivas especificaciones R/S,
cuando sea el caso, para todos los productos formados y diga cuáles son ópticamente activos.

iii.- Establezca las relaciones isoméricas y/o esteroisoméricas , entre todos los productos formados.

42.Respecto a la siguiente reacción:

 H3C CH3

I
AgNO3/ acetona - agua

H Reflujo

CH3
H3C HC H3C
3

Responder a las siguientes preguntas:

¿Cuál es la cinética de la reacción?

Proponga el mecanismo de reacción.

¿Qué efecto tendría aumentar la proporción de acetona, en la mezcla de solventes?

¿Qué efecto tendría sobre la proporción del producto, eliminar el AgNO3 de la mezcla de reacción.

43.The rate of elimination of cis-1-bromo-4-(1,1-dimethylethyl)cyclohexane is proportional to the

concentration of both substrate and base, but that of the trans isomer is proportional only to the
concentration of the substrate. Explain with structures and mechanism.

44.The isomer of 1,2,3,4,5,6-hexachlorocyclohexane shown in the margin undergoes E2 elimination

7000 times more slowly than any of its stereoisomers. Explain.
 ALQUENOS
45.Proponga el mecanismo de reacción considerando la estereoquímica de la
reacción entre el cis-3-hexeno y el Br2(CCl4).a 25ºC

46.Desarrollar el mecanismo de reacción del vinilciclopentano (ciclopentileteno) con agua en

medio ácido y calor para dar el-metilcilcohexanol como producto.

47.Tres isómeros C5H8 (A, B y C) reaccionan con Br2/CCl4 y no reaccionan con Na/NH3 (I).
AyB
dan pentano como producto al ser tratados con H2/Pd-C. En dichas condiciones C da un

compuesto D de fórmula C5H10.

48.Proponga estructuras adecuadas para A, B, C y D.

a. Trans  2  Br2(CCl4 )
buteno ⎯⎯⎯
Br2(ac)
b. Cis  2  penteno ⎯⎯
⎯⎯⎯⎯
c. Trans  2  KMnO4 (ac)/OH
penteno ⎯⎯⎯⎯ o
25 C
⎯⎯⎯
49.Tres Alquenos isómeros A, B y C tienen la fórmula global C5H8. Cada uno de ellos
absorbe sólo 1 equivalente de Hidrógeno en presencia de un catalizador adecuado
conduciendo al mismo producto saturado. Cuando se trata con HCl, los isómeros A y B
conducen a un único producto D (C5H9Cl). El compuesto C proporciona cuatro productos
al tratarlos con HCl, ninguno de los cuáles es idéntico a D.

a.- (2 ptos) Proponga estructuras y sus nombres correctos de A, B y C justificando su

comportamiento.

b.- (1 pto) Proponga el mecanismo de reacción de A o B (uno de los dos) cuando reacciona con
el HCl.
50.Productos para cada una de las siguientes reacciones. Considere la estereoquímica

51.Complete los productos de las siguientes reacciones, indicando el mayoritario en

aquellos casos en que pueda formarse más de uno.
 52.Dadas las siguientes secuencias de reacciones:

a) Indique las estructuras de los compuestos B, C y D.

b) Indique el mecanismo de la reacción de A para dar B.
53.Un compuesto (A), de fórmula general C4H6, es sometido a distintas reacciones con
los siguientes resultados:
a) Al ser hidrogenado en presencia de un catalizador de Pd/C absorbe dos equivalentes
de hidrógeno.
b) Al tratarse con sodio en amoníaco líquido se produce un compuesto iónico y se
desprende hidrógeno.
c) Al ser hidrogenado en presencia de un catalizador de Pd/C envenenado con BaSO4 y quinoleína
absorbe un equivalente de hidrógeno.
Deduzca la estructura de (A).
54.Complete las siguientes transformaciones:
55.Complete la siguiente secuencia sintética, indicando los productos
intermedios mayoritarios:

56.Suggest reasonable mechanisms for each of the following reactions. Use curved arrows to show
electron flow.

57.Two different compounds having the molecular formula C8H15Br are formed when 1,6-
dimethylcyclohexene reacts with hydrogen bromide in the dark and in the absence of peroxides.
The same two compounds are formed from 1,2-dimethylcyclohexene. What are these two
compounds?
58.On catalytic hydrogenation over a rhodium catalyst, the compound shown gave a mixture
containing cis-1-tert-butyl-4-methylcyclohexane (88%) and trans-1-tert-butyl-4-
methylcyclohexane (12%). With this stereochemical result in mind, consider the reactions in
(a) and (b).
(a) What two products are formed in the epoxidation of 4-tert-
butyl(methylene)cyclohexane? Which one do you think will predominate?
(b) What two products are formed in the hydroboration–oxidation of 4-tert-butyl(methylene)-
cyclohexane? Which one do you think will predominate?
 59.Catalytic hydrogenation of 1,4-dimethylcyclopentene yields a mixture of two products.
Identify them. One of them is formed in much greater amounts than the other (observed ratio
_10:1). Which one is the major product?
60.What two products can be formed by syn addition of hydrogen to 2,3-dimethylbicyclo[2.2.1]-2-
heptene?
61.Interpretar la eliminación E2 de Hofmann para el fluoruro de 2-flurohexano, comparado con los
otros 2-halohexanos en relación a los productos formados. Ref. pag. 956-946. Morrison y Boyd-
Quinta edición.
62.Se presentan las siguientes reacciones; tal como están escritas , para cada una, debe sumirse
son los productos principales o únicos. Diga si las reacciones son correctas o incorrectas,
justificar el fenómeno implicado.

a) H3 CH3 CH3 Cl
C CH CH CH2
+ HCl H3C CH CH CH3

CH3 CH3 OH
b) H3C CH CH CH2
+ Cl2 (ac) H3C CH CH CH2 Cl

c) + Br2 (CCl4) HH

Br Br

d) + CH2

HC
CHO
CHO

_
e) Cl + OH C(CH3)3

C(CH3)3
CH3
CH3

CH(CH3)2
CH
CH2
f)
HC CH(CH3)2
+
HC CN
HC CH(CH3)2 CN
CH CH(CH3)2
63.Proponga los productos principales formados en las siguientes reacciones de Diels-alder.

64.Complete la siguiente secuencia sintética, indicando los productos

intermedios mayoritarios:

65.Proponga las estructuras desde A hasta F, para la siguiente secuencia de reacciones:

66.Identificar los reactivos, condiciones y/o productos correspondientes a cada una de las
letras desde al A hasta la H en la siguiente secuencia de reacciones.
67.Complete las siguientes reacciones, considerando la estereoquímica e
identificando los reactivos y/o condiciones que representan las letras desde la (A)
hasta la (E).

68. Proponga el mecanismo de reacción para cada una de las reacciones

a. 1, 3  ⎯⎯⎯
Br2
Adición 1, 2 Adición 1, 4
butadieno ⎯⎯
(CCl4)
o

0 C

b. Desarrollar el mecanismo para la siguiente reacción:

 CH2OH
H2SO4 /
CH3
calor
CH3
69.El muscalure es la feromona sexual de la mosca casera. Tomando como
referencia la siguiente síntesis sugerida, partiendo de gas natural como única
fuente de acetileno y usando alcoholes de hasta 15 carbonos como únicas
fuentes de carbono muestre como sintetizar el muscalure.

n  C13H27C 
+  A (C15H27MgBr)
CH CH3CH2MgBr
A + n-C13H27Br  B (C23H44 )
H
B ⎯⎯⎯⎯⎯⎯⎯⎯⎯ 2
Catalizador de Lindlar (C23H46 )

70. Identificar las estructuras desde A hasta F.

71. Complete los reactivos que permiten efectuar las siguientes conversiones.
 CH3 C CH
CH3 C CH
12
CH3 CH CH 11 CH3 CH CH
2 2
OH OH
1 Cl Cl
10
H H

C O + C O CH3 CH CH
9 CH3 CH CH 2 2 2
2

H Br
CH
3 8
CH3 CH CH 3
2 2
OH 7 CH3 CH CH2
4
6
5 Cl Br
CH3 CH CH
3
Br
CH3 CH CH
2 CH CH CH3 CH2 CH3
CH 3 3
OH Br
OH
72. Proponga el mecanismo de reacción para la siguiente conversión.

ALCOHOLES
73.Write a chemical equation for the reaction of 1-butanol with each of the following:

(a) Sodium amide (NaNH2) (d) Phosphorus tribromide

(b) Hydrogen bromide, heat (e) Thionyl chloride

(c) Sodium bromide, sulfuric acid, heat

 74.Each of the following reactions has been described in the chemical literature and involves an
organic starting material somewhat more complex than those we have encountered so far.
Nevertheless, on the basis of the topics covered in this chapter, you should be able to write the
structure of the principal organic product of each reaction.

75.Select the compound in each of the following pairs that will be converted to the corresponding
alkyl bromide more rapidly on being treated with hydrogen bromide. Explain the reason for your
choice.

(a) 1-Butanol or 2-butanol

(b) 2-Methyl-1-butanol or 2-butanol

(c) 2-Methyl-2-butanol or 2-butanol

(d) 2-Methylbutane or 2-butanol

(e) 1-Methylcyclopentanol or cyclohexanol

(f ) 1-Methylcyclopentanol or trans-2-methylcyclopentanol

(g) 1-Cyclopentylethanol or 1-ethylcyclopentanol

76.Assuming that the rate-determining step in the reaction of 2-methyl-2-butanol with hydrogen
chloride to give 2-chloro-2-methylbutane is unimolecular, write an equation for this step. Use
curved arrows to show the flow of electrons.
77.Assuming that the rate-determining step in the reaction of 1-hexanol with hydrogen bromide to
give 1-bromohexane is an attack by a nucleophile on an alkyloxonium ion, write an equation for
this step. Use curved arrows to show the flow of electrons.
78.Two stereoisomers of 1-bromo-4-methylcyclohexane are formed when trans-4-
methylcyclohexanol reacts with hydrogen bromide. Write structural formulas of:

(a) trans-4-Methylcyclohexanol

(b) The carbocation intermediate in this reaction

(c) The two stereoisomers of 1-bromo-4-methylcyclohexane

79.Write the structure of the products that you expect from the reaction of 1-methylcyclohexanol with
(a) concentrated HCl and (b) concentrated H2SO4. Compare and contrast the mechanisms of the

- -
two processes. (Hint: Compare the relative nucleophilicity of Cl and HSO4 . Caution: When writing

mechanisms, use “arrow pushing” to depict electron fl ow; write out every step separately;
formulate complete structures, including charges and relevant electron pairs; and draw explicit
reaction arrows to connect starting materials or intermediates with their respective products.
Don’t use shortcuts, and don’t be sloppy!).

80.2-Methylcyclohexanol, on treatment with HBr, gives 1-bromo-1-methylcyclohexane. Explain by a

mechanism.
81. Predict the major product from the following

reactions: (a)2-Methyl-3-pentanol 1 H2SO4,

CH3OH solvent

82. Give a mechanism for the preceding reaction. Then predict the outcome of the reaction of 2-
chloro-4-methylpentane with methanol. (Hint: Try two successive hydride shifts to the most
stable carbocation.)
83. Molecules of the type A have been shown to dehydrate to B. Formulate a mechanism.
84. At 1000C, 3,3-dimethyl-2-butanol gives three products of E1 reaction: one derived from the
carbocation present prior to rearrangement, the other two from that formed after an alkyl shift
has taken place. Give the structures of these elimination products.
85. The product of the reaction of 5-bromo-3,3-dimethyl-1-pentanol with hydroxide is a cyclic ether.
Suggest a mechanism for its formation.
86. Bromoalcohol A transforms rapidly in the presence of sodium hydroxide to give the corresponding
oxacyclopropane, whereas its diastereomer B does not. Why? [Caution: Unlike the previous
problem, both substrates are trans-bromoalcohols.

87. You now know several ways of constructing an ether from an alcohol and a haloalkane. Which
approach would you choose for the preparation of (a) 2-methyl-2-(1-methylethoxy)butane; (b) 1-
methoxy-2,2-dimethylpropane? [Hint: The product for (a) is a tertiary ether, that for (b) is a
neopentyl ether.]

88. Give detailed mechanisms and fi nal products for the reaction of 3-methyl-2-pentanol with each
of the reagents that follow.

(a) NaH (b) Concentrated HBr (c) PBr3 (d) Concentrated H2SO4 at 130oC

(e) Dilute H2SO4 in (CH3)3COH

 89. Primary alcohols are often converted into bromides by reaction with NaBr in H 2SO4. Explain how
this transformation works and why it might be considered a superior method to that using
concentrated aqueous HBr.

90. What are the most likely product(s) of each of the following reactions?

91. Give the expected product(s) of the reaction of 1-pentanol with each of the following reagents.

(a) (CH3)3COK (b) Sodium metal (c) CH3Li (d) Concentrated HI

(e) Concentrated HCl (f) FSO3H (g) Concentrated H2SO4 at

o
(h) Concentrated H2SO4 130oC at 180 C (i) PBr3 (j) SOCl2

(k) K2Cr2O7 1 H2SO4 1 H2O (l) PCC, CH2Cl2 (m) (CH3)3COH 1 H2SO4 (as catalyst)

92. Give the expected product(s) of the reaction of trans-3-methylcyclopentanol

with each of the reagents in Problem 187.

93. Suggest a good synthetic method for preparing each of the following haloalkanes from the
corresponding alcohols.