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CURSO DE VERANO QUÍMICA ORGÁNICA II


2019-1
UNIDAD DE INSTRUCCIÓN NO 03
Desde aromaticidad hasta carbohidratos
1. Which of the following compounds are aromatic? Are any antiaromatic? (Hint: If possible, a
ring will be nonplanar to avoid being antiaromatic.)

2. Write the principal resonance structures of o-methylbenzyl cation and m-methylbenzyl cation.
Which one has a tertiary carbocation as a contributing resonance form?
3. Suggest an explanation for the observed order of SN1 reactivity of the following compounds.

4. A standard method for preparing sodium cyclopentadienide (C5H5Na) is by the reaction of


cyclopentadiene with a solution of NaNH2 in liquid ammonia. Write a net ionic equation for
this reaction, identify the acid and the base, and use curved arrows to track the flow of electrons.
5. The same anion is formed by loss of the most acidic proton from 1-methyl-1,3-
cyclopentadiene as from 5-methyl-1,3-cyclopentadiene. Explain.
6. (a) The calicene, so named because its shape resembles a chalice (calix is the Latin word for
“cup”). Both the electrostatic potential map and its calculated dipole moment (=4.3 D) indicate
that calicene is an unusually polar hydrocarbon. Which of the dipolar resonance forms, A or B,

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UNIDAD DE INSTRUCCIÓN NO 03
Desde aromaticidad hasta carbohidratos
better corresponds to the electron distribution in the molecule? Why is this resonance form
more important than the other?

(b) Which one of the following should be stabilized by resonance to a greater extent? (Hint:
Consider the reasonableness of dipolar resonance forms.)

7. Acridine is a heterocyclic aromatic compound obtained from coal tar that is used in the
synthesis of dyes. The molecular formula of acridine is C13H9N, and its ring system is
analogous to that of anthracene except that one CH group has been replaced by N. The two
most stable resonance structures of acridine are equivalent to each other, and both contain a
pyridine-like structural unit. Write a structural formula for acridine.
8. Give reagents suitable for carrying out each of the following reactions, and write the major
organic products. If an ortho, para mixture is expected, show both. If the meta isomer is the
expected major product, write only that isomer.

(a) Nitration of benzene (b) Nitration of the product of part (a)

(c) Bromination of toluene (d) Bromination of (trifluoromethyl)benzene

(e) Sulfonation of acetanilide (f) Chlorination of bromobenzene

(g) Friedel–Crafts alkylation of anisole with benzyl chloride

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(h) Friedel–Crafts acylation of benzene with benzoyl chloride

(i) Nitration of the product from part (h) (j) Sulfonation of anisole

9. Write a structural formula for the most stable cyclohexadienyl cation intermediate formed in
each of the following reactions. Is this intermediate more or less stable than the one formed
from benzene?

(a) Bromination of p-xylene (b) Chlorination of m-xylene

(c) Nitration of acetophenone

(d) Friedel–Crafts acylation of anisole with acetyl chloride

(e) Nitration of isopropylbenzene (f) Bromination of nitrobenzene

(g) Sulfonation of furan (h) Bromination of pyridine

10. In each of the following pairs of compounds choose which one will react faster with the
indicated reagent, and write a chemical equation for the faster reaction:

(a) Toluene or chlorobenzene with a mixture of nitric acid and sulfuric acid

(b) Fluorobenzene or (trifluoromethyl)benzene with benzyl chloride and aluminum chloride

(c) Methyl benzoate or phenyl acetate with bromine in acetic acid

(d) Acetanilide or nitrobenzene with sulfur trioxide in sulfuric acid

(e) p-Dimethylbenzene (p-xylene) or p-di-tert-butylbenzene with acetyl chloride and aluminum


Chloride

(f) Benzophenone or biphenyl (C6H5OC6H5) with chlorine and iron(III) chloride

11. Arrange the following five compounds in order of decreasing rate of bromination: benzene,
toluene, o-xylene, m-xylene, 1,3,5-trimethylbenzene (the relative rates are 2.107, 5.104, 5.102,
60, and 1).
12. Each of the following reactions has been carried out under conditions such that disubstitution
or trisubstitution occurred. Identify the principal organic product in each case.

(a) Nitration of p-chlorobenzoic acid (dinitration)

(b) Bromination of aniline (tribromination)


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(c) Bromination of o-aminoacetophenone (dibromination)

(d) Nitration of benzoic acid (dinitration)

(e) Bromination of p-nitrophenol (dibromination)

(f) Reaction of biphenyl with tert-butyl chloride and iron(III) chloride (dialkylation)

(g) Sulfonation of phenol (disulfonation)

13. Write equations showing how to prepare each of the following from benzene or toluene and
any necessary organic or inorganic reagents. If an ortho, para mixture is formed in any step of
your synthesis, assume that you can separate the two isomers.
(a) Isopropylbenzene (e) m-Chloroacetophenone

(b) p-Isopropylbenzenesulfonic acid (f) p-Chloroacetophenone

(c) 2-Bromo-2-phenylpropane (g) 3-Bromo-4-methylacetophenone

(d) 4-tert-Butyl-2-nitrotoluene (h) 2-Bromo-4-ethyltoluene

(i) 1-Bromo-3-nitrobenzene (n) 1-Phenyloctane

(j) 1-Bromo-2,4-dinitrobenzene (o) 1-Phenyl-1-octene

(k) 3-Bromo-5-nitrobenzoic acid (p) 1-Phenyl-1-octyne

(l) 2-Bromo-4-nitrobenzoic acid (q) 1,4-Di-tert-butyl-1,4-cyclohexadiene

(m) Diphenylmethane

14. How many products are capable of being formed from toluene in each of the following
reactions?

(a) Mononitration (HNO3, H2SO4, 40oC).

(b) Dinitration (HNO3, H2SO4, 80oC).

(c) Trinitration (HNO3, H2SO4, 110oC). The explosive TNT (trinitrotoluene) is the major

product obtained on trinitration of toluene. Which trinitrotoluene isomer is TNT?

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15. Of the groups shown, which is the most likely candidate for substituent X based on the partial
rate factors for chlorination? Propose the reaction mechanism for the chosen reagent

16. Each of the following reactions has been reported in the chemical literature and gives a
predominance of a single product in synthetically acceptable yield. Write the structure of the
product. Only monosubstitution is involved in each case, unless otherwise indicated.

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17. What combination of acyl chloride and arene would you choose to prepare each of the
following compounds by Friedel–Crafts acylation?

18. The partial rate factors for chlorination of biphenyl are as shown.

(a) What is the relative rate of chlorination of biphenyl compared with benzene?

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(b) If, in a particular chlorination reaction, 10 g of o-chlorobiphenyl was formed, how much
p-chlorobiphenyl would you expect to find?

19. Partial rate factors may be used to estimate product distributions in disubstituted benzene
derivatives. The reactivity of a particular position in o-bromotoluene, for example, is given by
the product of the partial rate factors for the corresponding position in toluene and
bromobenzene. On the basis of the partial rate factor data given here for Friedel–Crafts
acylation, predict the major product of the reaction of o-bromotoluene with acetyl chloride and
aluminum chloride.

20. When 2-isopropyl-1,3,5-trimethylbenzene is heated with aluminum chloride (trace of HCl


present) at 50_C, the major material present after 4 h is 1-isopropyl-2,4,5-
trimethylbenzene. Suggest a reasonable mechanism for this isomerization.

21. When a dilute solution of 6-phenylhexanoyl chloride in carbon disulfide was slowly added
(over a period of eight days!) to a suspension of aluminum chloride in the same solvent, it
yielded a product A (C12H14O) in 67% yield. Oxidation of A gave benzene-1,2-dicarboxylic
acid.

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Formulate a reasonable structure for compound A. Propose the reaction mechanism for the
first stage.

22. Show how you would make 1,3-dibromo-2-nitrobenzene from benzene.

23. Give the expected major product(s) of each of the following Reactions

24. Write the main product for monobromination of the following biphenyls. To determine the
main product. First consider the differences in reactivity between activators and deactivators
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and secondly the number of resonant structures that stabilize the intermediary. Indicate in each
case how many resonant structures stabilize the intermediary for the main product.

25. Perform the electrophilic attack of E + in positions 1 and 2 and develop the resonant structures
and the complex for each of the intermediaries of the benzonium ion formed and
argumentatively discuss which of the positions is favored for SeA?

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Problemas de espectroscopia
26. max for the n  * transition in ethylene is 170 nm. Is the HOMO–LUMO energy
difference in ethylene greater than or less than that of cis,trans-1,3-cyclooctadiene (230 nm)?

27. A solution of 4-methyl-3-penthen-2-one in ethanol has an absorbance of 0,52 to 236 nm in a


cell of path length of 1 cm. Its molar absorptivity in ethanol, at that wavelength, is 12,600 M-1
cm-1. What is the concentration of the compound?

28. A solution of nitrobenzene 4,03.10-5 M in hexane has 0,40 absorbance at 252 nm in a cell
with a path of 1 cm. What is the molar absorptivity of nitrobenzene in hexane to max = 252
nm?

29. a. to. At pH = 7, one of the ions shown below is violet and the other is blue. Which is which?

b. What would be the difference in the colors of the compounds at pH = 3?

30. 4-Methyl-3-penten-2-one has two absorption bands in its UV spectrum, one at 236 nm and
one at 314 nm.

a. Why are there two absorption bands? b. Which band has the highest absorbance?
31. How could UV spectroscopy be used to differentiate between the compounds of each of the
following pairs?

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32. Which band will find the highest wave number to. the stretching of the C-O of a phenol or the
stretching of the C-O of the cyclohexanol?

b. the stretching of the CwO of a ketone or the stretching of the CwO of an amide?

c. the stretching or flexing of the C-O bond in ethanol?

33. What functional group will have an absorption band at the highest wave number, a carbonyl
group bound to a carbon with sp3 hybridization or a carbonyl group bonded to a carbon with
hybridization sp2?
34. An oxygenated compound has an absorption band at, 1700 cm-1 and lacks bands of absorption
at, 3300 cm-1, 2700 cm-1 and a, 1100 cm-1. What kind of compound is it?
35. How could I distinguish IR spectroscopy between the following pairs of compounds? to.
a. A ketone and an aldehyde b. cis-2-hexene and trans-2-hexene
c. A cyclic ketone and an d-ketone. cyclohexene and cyclohexane
36. For each of the following pairs of compounds, indicate an absorption band that can be used to
differentiate them.

37. Which of the following compounds have a vibration that is inactive in infrared: acetone, 1-
butyne, 2-butyne, H2, H2O, Cl2 or ethene?

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38. Indicate three factors that influence the intensity of an IR absorption band.
39. The ultimate test of fluency in MS and IR is whether you can determine a moderately
complex structure from just the MS and the IR, with no additional information. The IR and
MS of a compound are shown below. Use everything you know about IR and MS, plus
reasoning and intuition, to determine a likely structure. Then show how your proposed
structure is consistent with these spectra.

40. Three IR spectra are shown, corresponding to three of the following compounds. For each
spectrum, determine the structure and explain how the peaks in the spectrum correspond to
the structure you have chosen.

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41. An unknown, foul-smelling hydrocarbon gives the mass spectrum and infrared spectrum
shown.

(a) Use the mass spectrum to propose a molecular formula. How many elements of
unsaturation are there?

(b) Use the IR spectrum to determine the functional group(s), if any.

(c) Propose one or more structures for this compound. What parts of the structure are
uncertain? If you knew that hydrogenation of the compound gives n-octane, would the
structure still be uncertain?

(d) Propose structures for the major fragments at 39, 67, 81, and 95 in the mass spectrum.
Explain why the base peak is so strong.

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42. A common lab experiment is the dehydration of cyclohexanol to cyclohexene.
(a) Explain how you could tell from the IR spectrum whether your product was pure
cyclohexene, pure cyclohexanol, or a mixture of cyclohexene and cyclohexanol. Give
approximate frequencies for distinctive peaks.
(b) Explain why mass spectrometry might not be a good way to distinguish cyclohexene from
cyclohexanol.
43. Four infrared spectra are shown, corresponding to four of the following compounds. For each
spectrum, determine the structure and explain how the peaks in the spectrum correspond to
the structure you have chosen.

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44. Apply the Woodward-fieser-kuhn-scott rules to determine the lmax of each of the following
chromophores

ob. =355 ob. =251

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ob. =314

45. Using the appropriate Woodward-Fieser rules calculate the expected λmax for each of the
following compounds:

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Rpta: a. 237 b. 259 c. 244 d. 303 e. 313 f. 318 g. 244 h. 382 i. 294 j. 254 k. 324 l. 239 m. 249 n. 244
(cross conj.) o. 407

46. Azulene and naphthalene are both C8H10 hydrocarbons, as shown. Azulene is blue and
naphthalene appears colorless. Which compound has the largest λmax? Which compound has
the smallest HOMO-LUMO π-molecular orbital energy difference?

Rpta: Azulene is colored in the visible region of the EM spectrum, so λmax must be the largest. The
most often observed transition is HOMO-LUMO, again with the longest wavelengths corresponding
to the lowest energy of transition, azulene has the lowest difference.

47. An unknown olefin shows a UV λmax = 231 nm (ε = 21,000) and three structures have been
proposed. Which is the most consistent with the UV data? Can this be solved using UV?
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Rpta: None of these are homoannular or heteroannular dienes, so the base wavelength is 214. Structure
2 has one exocyclic double bond and two alkyl substituents: 214 + 5 + (2 x 5) = 229; structure 3 has
one exo-cyclic double bond and two alkyl substituents: 215 + (2 x 5) = 229, so they cannot be discerned.
Structure 1 is held in the s-cis geometry and would have a λmax ~291 (271 base). Cannot be solved by
UV.

48. The UV of citral shows two maxima at 230 (ε = 11,500) and 320 nm (ε = 56). Identify the
chromophore and the type of electronic transition responsible for both absorptions.

Rpta: The chromophore is the unsaturated aldehyde, 230 nm for π  π*, and 320 nm for n  π*

49. Se sintetizó 89,568 miligramos 3-bromo-4-metilacetofenona. Para verificar si


realmente se obtuvo este compuesto se utilizó la técnica espectroscópica UV-Visible.
Se pretende construir la curva de calibración y para ello se prepararon una serie de
diluciones de diferente concentración con un estándar grado análisis (P.S.) de 3-
bromo-4-metilacetofenona que se analizaron a 260 nm y se obtuvieron los siguientes
resultados: Dato:  1,1cm
C (mol/L) 8,2.10-6 2,2.10-5 2,5.10-5 3,2.10-5 3,9.10-5 4,3.10-5 4,8.10-5

%T(260nm) 67,297% 34,594% 29,922% 21,330% 13,804% 12,531% 10,00%

Si los 0,8147 miligramos del producto obtenido en la síntesis se transfirieron a una fiola de
100 mL y se enrazaron con hexano, la respuesta obtenida en el espectrofotómetro para la
muestra a 260 nm presenta una absorbancia de A=0,8860. Según la información:
a) (2 ptos) Proponga la síntesis del 3-bromo-4-metilacetofenona, partiendo de benceno,
alcoholes de hasta dos carbonos como fuente de carbono y los reactivos necesarios.
b) (1 pto) Determine según las reglas de Scott, si la decisión de medir en max= 260 nm es
la decisión correcta. Explique. Se asume una desviación estándar de ±2nm

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c) (1 pto) Determine el coeficiente de extinción molar medio (  max ) para el compuesto.
d) (1.5 ptos) Discuta si la técnica espectroscópica confirma la síntesis del 3-
bromo-4-metilacetofenona. Justifique su respuesta.
Dato: Masa molar=212 g/mol

50. The IR spectrum of a compound of the overall formula C10H12O is shown below.
Propose 7 molecular vibrations of the IR spectrum and propose two possible structures,
compatible with the spectrum.

2.2 (1pto) Applying the prediction rules of maximum absorbance, establish  max and  max
for -caroteno.

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PROBLEMAS DE ALDEHIDOS Y CETONAS

51. Predict the product of the reaction of propanal with each of the following:
(a) Lithium aluminum hydride, followed by wáter (b) Sodium borohydride, methanol
(c) Hydrogen (nickel catalyst) (d) Methylmagnesium iodide, followed by dilute acid
(e) Sodium acetylide, followed by dilute acid (f) Phenyllithium, followed by dilute acid
(g) Methanol containing dissolved hydrogen chloride
(h) Ethylene glycol, p-toluenesulfonic acid, benzene (i) Aniline (C6H5NH2)
(j) Dimethylamine, p-toluenesulfonic acid, benzene (k) Hydroxylamine
(l) heated in triethylene glycol with sodium hydroxide (m) p-Nitrophenylhydrazine
(n) Semicarbazide (o) Chromic acid
52. Repeat the preceding problem for cyclopentanone instead of propanal.

53. Hydride reduction (with LiAlH4 or NaBH4) of each of the following ketones has been
reported in the chemical literature and gives a mixture of two diastereomeric alcohols in each
case. Give the structures of both alcohol products for each ketone.
(a) (S)-3-Phenyl-2-butanone
(b) 4-tert-Butylcyclohexanone

54. Choose which member in each of the following pairs reacts faster or has the more favorable
equilibrium constant for reaction with the indicated reagent. Explain your reasoning.

(c) Acetone or 3,3-dimethyl-2-butanone (equilibrium constant for cyanohydrin formation)


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(d) Acetone or 3,3-dimethyl-2-butanone (rate of reduction with sodium borohydride)

(e) CH2(OCH2CH3)2 or (CH3)2C(OCH2CH3)2 (rate of acid-catalyzed hydrolysis)

55. Equilibrium constants for the dissociation (Kdiss) of cyanohydrins according to the equation

56. Each of the following reactions has been reported in the chemical literature and gives a single
organic product in good yield. What is the principal product in each reaction?

57. Wolff–Kishner reduction (hydrazine, KOH, ethylene glycol, 130oC) of the compound shown
gave compound A. Treatment of compound A with m-chloroperoxybenzoic acid gave
compound B, which on reduction with lithium aluminum hydride gave compound C. Oxidation
of compound C with chromic acid gave compound D (C9H14O). Identify compounds A through
D in this sequence.

58. Compounds that contain both carbonyl and alcohol functional groups are often more stable as
cyclic hemiacetals or cyclic acetals than as open-chain compounds. Examples of several of
these are shown. Deduce the structure of the open-chain form of each.

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59. Compounds that contain a carbon–nitrogen double bond are capable of stereoisomerism much
like that seen in alkenes. The structures

are stereoisomeric. Specifying stereochemistry in these systems is best done by using E–Z descriptors
and considering the nitrogen lone pair to be the lowest priority group. Write the structures, clearly
showing stereochemistry, of the following:

(a) (Z)-CH3CHPNCH3 (b) (E)-Acetaldehyde oxime

(c) (Z)-2-Butanone hydrazone (d) (E)-Acetophenone semicarbazone

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60. Using ethanol as the source of all the carbon atoms, describe efficient syntheses of each of the
following, using any necessary organic or inorganic reagents:

61. Describe reasonable syntheses of benzophenone, from each of the following starting materials
and any necessary inorganic reagents.

(a) Benzoyl chloride and benzene

(b) Benzyl alcohol and bromobenzene

(c) Bromodiphenylmethane, (C6H5)2CHBr

(d) Dimethoxydiphenylmethane, (C6H5)2C(OCH3)2

(e) 1,1,2,2-Tetraphenylethene, (C6H5)2CNC(C6H5)2

62. Show a complete mechanism for this reaction.

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63. One of these reacts with dilute aqueous acid and the other does not. Give a mechanism for the
one that reacts, and show why this mechanism does not work for the other one.

64. Within each set of structures, indicate which will react fastest, and which slowest, toward
nucleophilic addition in basic conditions.

65. Show how you would accomplish the following syntheses efficiently and in good yield. You
may use any necessary reagents.

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66. Two structures of the sugar fructose are shown next. The cyclic structure predominates in
aqueous solution.

(a) Number the carbon atoms in the cyclic structure. What is the functional group at C2 in the cyclic
form?

(b) Propose a mechanism for the cyclization, assuming a trace of acid is present.

67. Show how you would synthesize the following derivatives from appropriate carbonyl
compounds.

68. Predict the products formed when cyclohexanone reacts with the following reagents.
(a) CH3NH2, H+ (b) excess CH3OH, H+

(c) hydroxylamine and weak acid


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(d) ethylene glycol and p-toluenesulfonic acid

(e) phenylhydrazine and weak acid

(f) Tollens reagent

(g) sodium acetylide, then mild H3O+

(h) sodium cyanide (l) acidic hydrolysis of the product from (k)

PROBLEMAS DE ACIDOS CARBOXÍLICOS

69. Of the two procedures just described, preparation and carboxylation of a Grignard reagent or
formation and hydrolysis of a nitrile, only one is appropriate to each of the following RX £
RCO2H conversions. Identify the correct procedure in each case, and specify why the other
will fail.

(a) Bromobenzene y benzoic acid

(b) 2-Chloroethanol y 3-hydroxypropanoic acid

(c) tert-Butyl chloride y 2,2-dimethylpropanoic acid

70. Propose methods for preparing butanoic acid from each of the following:
(a) 1-Butanol (b) Butanal

(c) 1-Butene (d) 1-Propanol

(e) 2-Propanol (f) Acetaldehyde

71. It is sometimes necessary to prepare isotopically labeled samples of organic substances for
probing biological transformations and reaction mechanisms. Various sources of the
radioactive mass-14 carbon isotope are available. Describe synthetic procedures by which
benzoic acid, labeled with 14C at its carbonyl carbon, could be prepared from benzene and the
following 14C-labeled precursors.

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72. You may use any necessary organic or inorganic reagents.

Give the product of the reaction of pentanoic acid with each of the following reagents:

(a) Sodium hydroxide (b) Sodium bicarbonate

(c) Thionyl chloride (d) Phosphorus tribromide

(e) Benzyl alcohol, sulfuric acid (catalytic amount)

(f) Chlorine, phosphorus tribromide (catalytic amount)

(g) Bromine, phosphorus trichloride (catalytic amount)

(h) Product of part (g) treated with sodium iodide in acetone

(i) Product of part (g) treated with aqueous ammonia

(j) Lithium aluminum hydride, then hydrolysis (k) Phenylmagnesium bromide

73. Show by a series of equations how you could synthesize each of the following compounds
from the indicated starting material and any necessary organic or inorganic reagents:

(a) 2-Methylpropanoic acid from tert-butyl alcohol

(b) 3-Methylbutanoic acid from tert-butyl alcohol

(c) 3,3-Dimethylbutanoic acid from tert-butyl alcohol

(d) HO2C(CH2) 5CO2H from HO2C(CH2) 3CO2H

74. When compound A is heated, two isomeric products are formed. What are these two
products?

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75. Explain about the number of signals that carbon dioxide presents in the IR spectrum.Explicar
por qué en la reacción de aldehídos con alcoholes en medio básico no hay formación de
acetales.
76. Develop the reaction mechanism of the desulfonation of p-toluenesulfonic acid.
77. Explain why the halogens as a substituent in benzene being deactivators in the electrophilic
aromatic substitution, acts as director -orto-, -para-.
78. Explain the increase in the selectivity of halogens in the substitution reaction via free radicals
in sand, compared to that of alkanes.
79. Through electronic transitions (level of molecular orbitals), explain the existence of color in
molecules.
80. Write all the reactions that can lead to the synthesis of the compounds, starting from benzene,
toluene or alcohols (up to three carbons) plus other necessary inorganic reagents.

81. Explain by composition the difference in acidity between p-nitrobenzoic acid and m-
nitrobenzoic acid.
82. You have 12 grams of a sample of a fat that contains 1.2 grams of a free fatty acid. Knowing
that the acidity index of the sample is 20.18 mg KOH / g fat. Among the acids shown below
represents the structure of the possible free acid present in the sample.
Data: Palmitoleic acid (C16: 1), Palmitic acid (C16: 0), Oleic acid (C18: 1), Linoleic acid (C18: 2),
Linolenic acid (C18: 3 w3), EPA (C20: 5 w3) , DHA (C22: 6 w3).

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83. Identificar el nombre de cada función química que se le presenta a continuación y completar las
reacciones que conducen a su formación a partir de un compuesto carbonílico. Proponga el
mecanismo de reacción para la formación de un cetal.

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84. Según el art. 525 del CAA los aceites refinados deben presentar un IA inferior a 6 mg
de KOH / g de muestra.
Volumen de NaOH 0,5 N
Muestra Masa muestra % Acido oleico
f=1,0000

Aceite I 1,7500 g 0,3 mL -

Aceite II 1,3200 g 0,6 mL -

Aceite III - - 0,9

Datos: Acido oleico (C18:1)


b) Expresar el límite máximo de IA dado en el CAA como % de ácido oleico

85. Una fábrica de aceite de oliva procesa, bajo las mismas condiciones, dos partidas de
frutos de distintos proveedores, obteniendo dos lotes de aceite (A y B)
a) Determinar, en base al IA, si los lotes de aceite de oliva podrán comercializarse como
virgen extra. Se presentan los datos experimentales para determinar el IA de ambos aceites.
VNaOH= 0,05 N
Muestra Masa muestra
f=0,9888
Aceite A 1,6040 g 0,9 mL
Aceite B 1,2532 g 1,7 mL
b) Podría sacar alguna conclusión respecto de la calidad de la materia prima. Justifique su
respuesta.
Dato: CAA, art.535: regula los valores de acidez libre para distintos tipos de aceite de oliva
virgen:
Clase extra: máx. 2 mg de KOH / g
Clase fina: máx. 2 % como ácido oleico
Clase común: máx. 6,60 mg de KOH / g

86. Se tiene una muestra de un aceite que contiene 2 % de ácido oleico y 3 % de un ácido graso libre
desconocido. Para neutralizar el ácido libre contenido en 12 gramos de aceite de este aceite se
requirió 4,3 mL de NaOH 0,475 N. Determinar el índice de acidez y represente la estructura del
correspondiente ácido graso desconocido.
Dato: Ácido oleico C18:1, Ácido linoleico C18:2 6 Ácido linolénico C18:3 3
EPA C20:5 3 DHA C22:6 3 Ácido esteárico C18:0

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87. When benzoic acid is allowed to stand in water enriched in 18O, the isotopic label becomes
incorporated into the benzoic acid. The reaction is catalyzed by acids. Suggest an explanation
for this observation.

SEMANA 27 DE MAYO AL 01 DE JUNIO

1. Se tiene 13 gramos de un aceite de pescado constituida por 90 % de un triglicérido


(formado por un solo tipo de ácido graso), 3,2% de ácido graso libre (el mismo ácido
graso del triglicérido) y 6,8 % de materia insaponificable. Esta muestra de aceite se
dispersa en 100 mL de alcohol absoluto y se añade 30 mL de NaOH 1, 5 N,
sometiéndolo a reflujo por 45 minutos. Después de enfriar la solución saponificada se
adicionó 3 gotas fenolftaleína y se retrovaloró con HCl, alcanzando el punto de
equivalencia con la adición de 25 mL de HCl 0,375 N. Detemine:
a. El índice de saponificación b. Represente la estructura del triglicérido
Dato: Ar : H = 1, 0; O = 16, 0; Na = 23, 0; K = 56,1
Acido palmitoleico (C16:1), Acido palmítico (C16:0), Ácido oleico (C18:1), Acido linoleico (C18:2),
Acido linolénico (C18:3 w3), EPA (C20:5 w3), DHA (C22:6 w3).

2. El valor estándar aceptado para el índice de saponificación del sebo es 140,213 mg


NaOH/g sebo, con una desviación estándar de 0,003. Se desea validar el índice de
saponificación de un sebo en el laboratorio de Química con un nivel de confianza del
95 %. Se encargó a cinco estudiantes del laboratorio efectuar las determinaciones del
índice de saponificación y se replicaron cinco muestras de sebo que se dispersaron
en 61 mL de NaOH de concentración de 0,101 N y después de refluir por 30 minutos
se procedió a retrovalorar con HCl 0,051 N, reportándose los siguientes datos. Ar :
H=1, O=16, Na=23, K=39,1.
Experimento Masas de sebo Volumen de HCl 0,051 N
Estudiantes 1 1,002 g 49,636 mL
Estudiante 2 1,561 g 11,448 mL
Estudiante 3 0,980 g 51,318 mL
Estudiante 4 1,2112g 35,439 mL
Estudiante 5 0,997 g 55,177 mL

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a. Discuta si los cinco valores deben ser aceptados para el análisis respectivo.
b. Determine el índice de saponificación con un nivel de confianza del 95 %.
c. Discuta si el índice de saponificación hallado es aceptado frente al valor estándar.
Dato: Ar : H = 1, 0; O = 16, 0; Na = 23, 0; K = 56,1

3. Give the structure of the expected product of the following reaction:

4. Compare N-methylacetamide (see the preceding paragraph) with its amide isomers
propanamide and N,N-dimethylformamide. Which do you predict has the highest
boiling point? The lowest?

5. Write an equation showing the preparation of the following amides from the indicated
carboxylic acid derivative:

6. Propose the mechanism of reaction in acid medium and in basic medium

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7. Penicillin-resistant strains of bacteria contain _-lactamases, enzymes that catalyze the
hydrolysis of a penicillin before the penicillin can acylate transpeptidase. Suggest a
reasonable structure for the product C16H20N2O5S formed by lactamase-catalyzed
hydrolysis of penicillin G.

8. Write a structural formula for the principal organic product or products of each of the
following reactions:
(a) Acetyl chloride and bromobenzene, AlCl3
(b) Propanoyl chloride and sodium propanoate
(c) Butanoyl chloride and benzyl alcohol
(d) p-Chlorobenzoyl chloride and ammonia

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9. On being heated with a dilute solution of sulfuric acid in water, the compound shown was
observed to liberate CO2. What organic compound is formed during the reaction?

10. Using toluene, sodium cyanide, and carbon dioxide as the sources of the carbon atoms, along
with any necessary inorganic reagents, show how you could prepare each of the following:
(a) Benzoyl chloride (f) Benzyl cyanide
(b) Benzoic anhydride (g) Phenylacetic acid
(c) Benzyl benzoate (h) p-Nitrobenzoyl chloride
(d) Benzamide (i) m-Nitrobenzoyl chloride
(e) Benzonitrile

11. When compounds of the type represented by A are allowed to stand in pentane, they are
converted to a constitutional isomer B.

Hydrolysis of either A or B yields RNHCH2CH2OH and p-nitrobenzoic acid. Suggest a reasonable


structure for compound B, and demonstrate your understanding of the mechanism of this reaction by
writing the structure of the key intermediate in the conversion of compound A to compound B.

12. (a) In the presence of dilute hydrochloric acid, compound A is converted to a constitutional
isomer, compound B.

Suggest a reasonable structure for compound B.


(b) The trans stereoisomer of compound A is stable under the reaction conditions. Why does
it not rearrange?
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13. Si una muestra de aceite de oliva está formada por 50 % de oleína (trioleina), materia
insaponificable y restos de ácido oleico libre y 10 % de un triglicérido formado por dos
unidades de graso X y 1 unidad de ácido oleico. Para neutralizar el ácido libre contenido en
12 gramos de aceite de oliva se requirió 10 mL de NaOH 0,0383 N. Para determinar el índice
de saponificación se utilizó 10 gramos de aceite de oliva requiriéndose 40 mL de KOH 0,5174
N para alcanzar el punto final. Determinar:
Dato: Acido palmitoleico (C16:1), Acido palmítico (C16:0), Ácido oleico (C18:1), Acido esteárico
(C18:0), Acido linoleico (C18:2), Acido linolénico (C18:3 w3), EPA (C20:5 w3), DHA (C22:6 w3).
a) Índice de acidez y su correspondiente clasificación.
b) Índice de saponificación
c) La estructura y el nombre del triglicérido desconocido
d) El porcentaje de materia insaponificable
Dato: Ar : H = 1, 0; O = 16, 0; Na = 23, 0; K = 56,1

14. Se tiene 13 gramos de un aceite de pescado constituida por 90 % de un


triglicérido (formado por un solo tipo de ácido graso), 3,2% de ácido graso libre (el
mismo ácido graso del triglicérido) y 6,8 % de materia insaponificable. Esta muestra
de aceite se dispersa en 100 mL de alcohol absoluto y se añade 30 mL de NaOH 1, 5
N, sometiéndolo a reflujo por 45 minutos. Después de enfriar la solución saponificada
se adicionó 3 gotas fenolftaleína y se retrovaloró con HCl, alcanzando el punto de
equivalencia con la adición de 25 mL de HCl 0,375 N. Detemine:
b. El índice de saponificación b. Represente la estructura del triglicérido
Dato: Ar : H = 1, 0; O = 16, 0; Na = 23, 0; K = 56,1
Acido palmitoleico (C16:1), Acido palmítico (C16:0), Ácido oleico (C18:1), Acido linoleico
(C18:2), Acido linolénico (C18:3 w3), EPA (C20:5 w3), DHA (C22:6 w3).

15. Se tiene 12 gramos de una muestra de una grasa que contiene 1,2 gramos de un ácido graso
libre. Sabiendo que el índice de acidez de la muestra es 20,18 mg KOH/g grasa. Entre los ácidos
mostrados a continuación represente la estructura del posible ácido libre presente en la muestra.
Dato: Acido palmitoleico (C16:1), Acido palmítico (C16:0), Acido oleico (C18:1),
Acido linoleico (C18:2), Acido linolénico (C18:3 w3), EPA (C20:5 w3), DHA (C22:6 w3).
Rpta: Ácido linolénico

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16. Un aceite presenta masas iguales de dos triglicéridos A y B y 6,5 % de ácido oleico libre (C18:1).
El triglicérido A está formado por dos unidades de ácido oleico (C18:1) y una de ácido láurico
(C12:0); en tanto que, el triglicérido B está formado por una unidad de ácido laúrico (C12:0), una
de palmítico (C16:0) y una de un ácido graso insaturado desconocido. Sabiendo que el índice de
saponificación de la muestra es 206,75 mg KOH/g muestra, determine el nombre de ácido graso
desconocido que constituye al triglicérido B.

a) Índice de acidez
b) Identifique el nombre del ácido graso desconocido presente en el triglérido B.
c) Escriba la estructura del triglicérido
Rpta: I.A. = 12,93 mgKOH/g muestra
El ácido es DHA

CARBANIONES

104. Find the most acidic hydrogen in each of the following and write a chemical equation
for the proton-transfer process that occurs on reaction with hydroxide ion. Use curved
arrows to show electron flow and label the acid, base, conjugate acid, and conjugate
base.
(a) tert-Butyl methyl ketone (c) Cyclohexanone
(b) 3-Methylbutanal

105. Write the structure of the enolate ion derived from each of the following _-dicarbonyl
compounds. Give the three major resonance contributors of each enolate.
(a) 2-Methyl-1,3-cyclopentanedione
(b) 1-Phenyl-1,3-butanedione

106. Methyllithium is a stronger base than lithium diisopropylamide but would not be a good
choice for converting aldehydes and ketones to their enolates. Can you think of a reason why?

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107. Write the structure of the aldol addition product of

108. Write the structure of the aldol condensation product of each of the aldehydes in the
previous problem. One of these aldehydes can undergo aldol addition, but not aldol
condensation. Which one? Why?

109. Outline a synthesis of 2-ethyl-1-hexanol from butanal.


110. Give the structure of the mixed aldol condensation product of benzaldehyde with

111. Write structural formulas corresponding to


(a) The enol form of 2,4-dimethyl-3-pentanone
(b) The enol form of acetophenone
(c) The two enol forms of 2-methylcyclohexanone

112. Write structural formulas corresponding to

113. Chlorination of 2-butanone yields two isomeric products, each having the molecular
formula C4H7ClO. Identify these two compounds.

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114. In each of the following pairs of compounds, choose the one that has the greater enol
content, and write the structure of its enol form:

115. Each of the following reactions has been reported in the chemical literature. Write the
structure of the product(s) formed in each case.

116. Show how each of the following compounds could be prepared from 3-pentanone. In
most cases more than one synthetic transformation will be necessary.
(a) 2-Bromo-3-pentanone
(b) 1-Penten-3-one
(c) 1-Penten-3-ol
(d) 3-Hexanone
(e) 2-Methyl-1-phenyl-1-penten-3-one

117. Each of the following reactions has been reported in the chemical literature. Write the
structure of the product(s) formed in each case.
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118. (a) A synthesis that begins with 3,3-dimethyl-2-butanone gives the epoxide shown.
Suggest reagents appropriate for each step in the synthesis.

(b) The yield for each step as actually carried out in the laboratory is given above each arrow.
What is the overall yield for the three-step sequence?
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119. Consider the ketones piperitone, menthone, and isomenthone.

Suggest reasonable explanations for each of the following observations:

(a) Optically active piperitone ([]=+32o) is converted to racemic piperitone on standing in


a solution of sodium ethoxide in ethanol.
(b) Menthone is converted to a mixture of menthone and isomenthone on treatment with 90%
sulfuric acid.

AMINAS

120. As the extent of electron delocalization into the ring increases, the geometry at
nitrogen flattens. p-Nitroaniline, for example, is planar. Write a resonance contributor for p-
nitroaniline that shows how the nitro group increases electron delocalization.

121. The pKa’s of the conjugate acids of the two amines shown differ by a factor of 40,000.
Which amine is the stronger base? Why?

122. Each of the following is a much weaker base than aniline. Present a resonance
argument to explain the effect of the substituent in each case.
(a) o-Cyanoaniline (b) acetanilide (c) p-Aminoacetophenone

123. Write the acid-base reaction for each of the alacaloids in dilute hydrochloric acid.

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124. Alkylation of ammonia is sometimes employed in industrial processes; the resulting


mixture of amines is separated by distillation. The ultimate starting materials for the industrial
preparation of allylamine are propene, chlorine, and ammonia. Write a series of equations
showing the industrial preparation of allylamine from these starting materials. (Allylamine
has a number of uses, including the preparation of the diuretic drugs meralluride and
mercaptomerin.)
125. Outline syntheses of each of the following arylamines from benzene:
(a) o-Isopropylaniline (d) p-Chloroaniline
(b) p-Isopropylaniline (e) m-Aminoacetophenone
(c) 4-Isopropyl-1,3-benzenediamine

126. Show how you could prepare each of the following amines from benzaldehyde by
reductive amination:
(a) Benzylamine (c) N,N-Dimethylbenzylamine
(b) Dibenzylamine (d) N-Benzylpiperidine

127. Outline syntheses of each of the following from aniline and any necessary organic or
inorganic reagents:
(a) p-Nitroaniline (b) 2,4-Dinitroaniline (c) p-Aminoacetanilide
128. Design a synthesis of m-bromophenol from benzene.
129. Show how you could prepare m-bromoiodobenzene from benzene.
130. Show the proper sequence of synthetic transformations in the conversion of benzene to
ethyl m-fluorophenyl ketone.
131. Cumene (isopropylbenzene) is a relatively inexpensive commercially available starting
material. Show how you could prepare m-isopropylnitrobenzene from cumene.

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132. What amine and what diazonium salt would you use to prepare chrysoidine?

133. Arrange the members of each group in order of decreasing basicity:


(a) Ammonia, aniline, methylamine
(b) Acetanilide, aniline, N-methylaniline
(c) 2,4-Dichloroaniline, 2,4-dimethylaniline, 2,4-dinitroaniline
(d) 3,4-Dichloroaniline, 4-chloro-2-nitroaniline, 4-chloro-3-nitroaniline
(e) Dimethylamine, diphenylamine, N-methylaniline
134. Physostigmine, an alkaloid obtained from a West African plant, is used in the
treatment of glaucoma. Treatment of physostigmine with methyl iodide gives a quaternary
ammonium salt. What is the structure of this salt?

135. Describe procedures for preparing each of the following compounds, using ethanol as
the source of all their carbon atoms. Once you prepare a compound, you need not repeat its
synthesis in a subsequent part of this problem.
(a) Ethylamine
(b) N-Ethylacetamide
(c) Diethylamine
(d) N,N-Diethylacetamide
(e) Triethylamine
(f) Tetraethylammonium bromide
136. Show by writing the appropriate sequence of equations how you could carry out each
of the following transformations:
(a) 1-Butanol to 1-pentanamine
(b) tert-Butyl chloride to 2,2-dimethyl-1-propanamine
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(c) Cyclohexanol to N-methylcyclohexylamine
(d) Isopropyl alcohol to 1-amino-2-methyl-2-propanol
(e) Isopropyl alcohol to 1-amino-2-propanol

137. Give the structure of the expected product formed when benzylamine reacts with each
of the following reagents:
(a) Hydrogen bromide
(b) Sulfuric acid
(c) Acetic acid
(d) Acetyl chloride
(e) Acetic anhydride
(f) Acetone
(g) Acetone and hydrogen (nickel catalyst)
(h) Ethylene oxide
(i) 1,2-Epoxypropane
(j) Excess methyl iodide
(k) Sodium nitrite in dilute hydrochloric acid
138. Write the structure of the product formed on reaction of aniline with each of the
following:
(a) Hydrogen bromide
(b) Excess methyl iodide
(c) Acetaldehyde
(d) Acetaldehyde and hydrogen (nickel catalyst)
(e) Acetic anhydride
(f) Benzoyl chloride
(g) Sodium nitrite, aqueous sulfuric acid, 0–5_C
(h) Product of part (g), heated in aqueous acid
(i) Product of part (g), treated with copper(I) chloride
(j) Product of part (g), treated with copper(I) bromide
(k) Product of part (g), treated with copper(I) cyanide
(l) Product of part (g), treated with hypophosphorous acid
(m) Product of part (g), treated with potassium iodide
(n) Product of part (g), treated with fluoroboric acid, then heated
(o) Product of part (g), treated with phenol
(p) Product of part (g), treated with N,N-dimethylaniline
139. Write the structure of the product formed on reaction of acetanilide with each of the
following:
(a) Lithium aluminum hydride, followed by water
(b) Nitric acid and sulfuric acid
(c) Sulfur trioxide and sulfuric acid

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(d) Bromine in acetic acid
(e) tert-Butyl chloride, aluminum chloride
(f) Acetyl chloride, aluminum chloride
(g) 6 M hydrochloric acid, reflux
(h) Aqueous sodium hydroxide, reflux

140. Each of the following compounds has been prepared from p-nitroaniline. Outline a
reasonable series of steps leading to each one.
(a) p-Nitrobenzonitrile (d) 3,5-Dibromoaniline
(b) 3,4,5-Trichloroaniline (e) p-Acetamidophenol (acetaminophen)
(c) 1,3-Dibromo-5-nitrobenzene
141. Each of the following compounds has been prepared from o-anisidine (o-
methoxyaniline).
Outline a series of steps leading to each one.
(a) o-Bromoanisole (d) 3-Fluoro-4-methoxybenzonitrile
(b) o-Fluoroanisole (e) 3-Fluoro-4-methoxyphenol (c) 3-Fluoro-4-methoxyacetophenone
142. (a) Outline a synthesis of the following compound from nitrobenzene, p-nitrobenzyl
alcohol, and any necessary organic or inorganic reagents.
(b) How would you modify the synthesis if you had to start with p-nitrotoluene instead
of p-nitrobenzyl alcohol?
143. Design syntheses of each of the following compounds from the indicated starting
material and any necessary organic or inorganic reagents:
(a) p-Aminobenzoic acid from p-methylaniline
(b) (c) 1-Bromo-2-fluoro-3,5-dimethylbenzene from m-xylene

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144. N, N-Dimethylaniline and pyridine are similar in basicity, whereas 4-(N,N-
dimethylamino)pyridine is considerably more basic than either. Apply resonance principles to
identify the more basic of the two nitrogens of 4-(N,N-dimethylamino) pyridine, and suggest
an explanation for its enhanced basicity.

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CURSO DE VERANO QUÍMICA ORGÁNICA II
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Desde aromaticidad hasta carbohidratos
145. The compound shown is a somewhat stronger base than ammonia. Which nitrogen do
you think is protonated when it is treated with an acid? Write a structural formula for the
species that
results

146. Partiendo de benceno y los reactivos necesarios, muestre como sintetizar:

a) 2-bromo-4-nitroanilina. b) 1,3,5-tribromobenceno

c) m-bromotolueno a) p-bromofenol

b) o-bromotolueno (único producto principal)

147. El colorante azoico Acid Brown (I) es utilizado para proporcionar tonos apagados de
color marrón. Partiendo de benceno y el ácido -aminonaftalensufónico (II) mostrar como
sintetizar el colorante azoico Acid Brown.

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148. El azul negro de naftol 6B (negroamido 10B) es un colorante azoico ácido de la lana
más importante para tintes negros, de una estabilidad moderada. Partiendo de benceno y ácido
H, muestre como sintetizar el colorante azoico

OH NH2
N N NO 2
N N

NaO 3S SO3Na

Azul negro de naftol 6B

OH NH2

NaO 3S SO3Na
Ácido H

149. A continuación se muestra una amida del ácido 1H-pirrolo (3,2-b(piridin-3-carboxílico


(I) que se enlazan al sitio de benzodiazepina de los receptores GABAA. Tales compuesto
pueden usarse para modular el enlace del ligando a los receptores GABAA in vivo e in vitro, y
son particularmente útiles en el tratamiento de una variedad de trastornos del sistema nervioso
central (SNC) en humanos, animales de compañía domesticados, y animales de ganado.

a) Escriba la reacción de I con el ácido clorhídrico diluido.


b) Proponga el mecanismo de reacción de la hidrólisis de la amida en medio ácido.

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(I)
150. El negro oscuro directo E, es el colorante triazoico negro más ampliamente utilizado. Se
prepara de la bencidina bisdiazotada por copulación con 1 mol de ácido H en medio ácido,
después 1 mol de cloruro de becenodiazonio en el resto del ácido H en medio alcalino y
finalmente por copulación del segundo grupo diazonio de la bencidina con la m-fenilendiamina
(m-bencenodiamino).

NH2 OH
N N N N N
H2N N

NaO 3S SO3Na
NH2
Negro oscuro directo E

NH2 OH

NaO 3S SO 3Na

ácido H

 Escribir la estructura de los sistemas fuertemente activados y las sales de diazonio


implicados en la formación del colorante negro oscuro directo E.
 Partiendo de benceno y ácido H, proponga una síntesis del colorante.

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151. Partiendo de benceno y -naftol, como única fuente de carbono y los reactivos
necesarios, muestre las reacciones que permiten sintetizar el siguiente colorante azoico:

N Cl
N
OH OH

- naftol Colorante azoico

152. Se dispone de nitrobenceno marcado con el isótopo 14C (  ) en la posición indicada.


Diseñar las rutas sintéticas (A hasta D) a partir de nitrobenceno marcado, para obtener los
derivados clorobencénicos mostrados

Br Br

B Br
Br
A C
Br NO 2 Br

Br
D

Br Br

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CURSO DE VERANO QUÍMICA ORGÁNICA II
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Desde aromaticidad hasta carbohidratos

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