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Chapter 8
 Bonds as Nucleophiles:
Reactions of Alkenes, Alkynes, Dienes, and Enols
CHECKPOINT PROBLEMS
Practice Problem 8.1
a)
First, add the H atoms around the double bond and identify the roles of the reagents.
Now, draw mechanistic arrows to show the flow of electrons from the nucleophile to the
electrophile. Be sure to direct the arrow toward the δ+ part of the electrophile and continue to
push the electron pairs to the ultimate electron sink (Cl–).
Next, draw the products of this step, using the arrows to determine the products.
There is no preference as to which carbon the H adds to, since cyclohexene is symmetrical.
Now, repeat the process for the new set of intermediate reactants.
Redraw the steps to show the total mechanism, leaving out added lone pairs and hydrogens.
b)
First, identify the reagents adding H atoms to the alkene and add mechanistic arrows to show
electron flow from the nucleophilic π–bond to the electrophile.
The resulting products would be
Reacting the intermediate nucleophile (Nu) and electrophile (E) gives the final product.
The overall reaction mechanism would be
c)
Leaving out the lone pairs this time to avoid clutter, the two reagents are the nucleophilic
alkene Nu and the electrophilic hydrogen on E. Donating the π-electrons to the H gives
H O H O
+ H O S OH + O S OH
H O H O
H
Nu E
The second step in the reaction is the nucleophilic, charged oxygen on the hydrogen sulfate
ion donating electrons to the charged carbon in the electrophilic carbocation.
8-2 Copyright © 2018 Nelson Education Limited

The overall mechanism would be
d)
Add H atoms to the alkene and expand the structure of the carboxylic acid. Then, react the
alkene π electrons with the electrophilic H atom in the acid.
The next step is the carboxylate anion reacting with the positive carbocation.
Putting it all together would give the overall mechanism

O
O O
+ + O CF3
H O CF3 O CF3
Integrate the Skill 8.2
a)
Since this diene is symmetric, the same initial carbocation products will form regardless
of which double bond you choose. The possibility for different carbocations comes from
reacting either end of the alkene with the acidic proton. Picking the top double bond
arbitrarily gives two products shown below, with the added H atom shown for clarity.
The top one has the resonance forms indicated and would be the most stable.
Copyright © 2018 Nelson Education Limited 8-3

b)
As in part (a), the symmetry here means reacting either double bond will result in the same
set of products.
a) This alkene is asymmetric, so two possible carbocation intermediates can form.
The tertiary carbocation is more stable and most of the reaction will proceed through this
intermediate.

b) Here, secondary and tertiary carbocation intermediates are possible leading to two products.
tertiary carbocation
+ Cl
Cl
+ major
H Cl
+
Cl
Cl
minor
secondary carbocation
The major product goes through the more stable tertiary intermediate.
c) This alkene is symmetric, so only one possible intermediate forms, leading to one product.
d) The asymmetric alkene has two possible intermediate carbocations.
The major product forms through the more stable tertiary carbocation intermediate.

e) The asymmetric alkene will form two different carbocation intermediates, as shown below.
The secondary carbocation will be preferred and lead the major product indicated.
a) This is a symmetric diene, so reaction of one or the other double bond would lead to the
same products. Considering reacting just one double bond leads to the following possible
reaction pathways. Both reactions generate secondary carbocations as intermediates.
The top reaction proceeds through a resonance-stabilized intermediate, but reaction of either
resonance form leads to the same final product. This is the favoured pathway, as this would
be the most stable carbocation and therefore the one that will be formed most rapidly.
The bottom reaction leads to the product shown, which would be the minor product.

b) This is a symmetric diene, so reacting either double bond would lead to the same products.
Both pathways proceed through secondary carbocations.
The bottom pathway will be favoured due to the more stable resonance-stabilized
carbocation, which will be formed more rapidly than the secondary carbocation of the top
pathway. Two products result from this pathway, since the carbocation sites in the resonance
forms are not symmetric. A third, distinct, minor product is formed via the bottom pathway,
as indicated.
c) To simplify the diagrams, consider the reaction of each double bond separately. The first
bond would proceed through two secondary carbocation intermediates and lead to the two
products shown.
Reaction of the other double bond would also proceed through two pathways each, with a
secondary carbocation intermediate, as shown.
Br
+
O Br O
+ H Br
O
Br
+
Br
O O
use most significant major product

resonance contributor
in mechanisms O
The choice of major product is due to the resonance stabilization of the carbocation in the
bottommost reaction pathway. This is the most stable carbocation and would lead to the
formation of the major product.

a) The reaction proceeds through two carbocations of very different stability. Since primary
carbocations are less stable than tertiary carbocations, the bottom pathway would be
preferred and result in the major product.
b) Here, the bottom pathway proceeds though a secondary carbocation, which is more stable
than the primary carbocation in the upper reaction intermediate. The secondary carbocation
would form faster and lead to the major product, as indicated.

c) The two carbocation intermediates are secondary and tertiary respectively. Tertiary being
more stable. the bottom reaction will be favoured and lead to the major product shown.
d) The possible reaction pathways for this substrate are shown below.
primary carbocation
slow
O O
+ Br Br
O minor
+ H Br
O O
+ Br
fast Br
major
resonance stabilized use most significant

secondary carbocation resonance forms in mechanisms
The most favourable pathway is the bottom one, with the more stable resonance-stabilized
secondary cation intermediate. This leads to the major product indicated.

The products of HCl addition to each substrate (A–C) need to be considered separately.
fast
Cl
+
O Cl O
+ H Cl major
O (desired product)
A
+
O Cl O Cl
slow
minor
primary carbocation
Substrate A has two possible products, as shown, but the favoured one is the desired product. A
would be a good choice to make the required molecule.
fast
Cl
+
O Cl O
major
+ H Cl (desired product)
O
Cl
B
+
O Cl O
slow
minor
Substrate B also produces the desired molecule as the major product.

The reaction of substrate C is shown below.
slow Cl
O O
+
Cl
minor
O + (desired product)
H Cl
Cl
C
O O
+
Cl
fast
major
O
resonance-stabilized
Although the desired product could form, it would not be the favoured reaction pathway.
The bottom reaction pathway is preferred due to the resonance stabilization of the secondary
carbocation, as shown.
So, compounds A and B would be the best molecules to use.
a) Sulphuric acid is strong, so it will be completely dissociated in aqueous solution.
The hydronium ion will be the electrophile reacting with the alkene.
Water will then be the nucleophile reacting with the carbocation.
The protonated alcohol is deprotonated by water, regenerating the hydronium ion.
Overall reaction
H 2O
OH
H2SO4

b) Phosphoric acid is a strong acid and will protonate the basic alcohol group to some extent.
The protonated alcohol group will be the electrophile reacting with the alkene.
Ethanol will then be the nucleophile reacting with the carbocation.
The protonated ether is deprotonated by alcohol regenerating the protonated alcohol.
Overall reaction
EtOH
OEt
H3PO4
c) Sulfuric acid will react with the double bond to generate a tertiary carbocation.
The alcohol group in the molecule is the best nucleophile available and will react with the
carbocation.
The slightly basic hydrogen sulphate ion will deprotonate the ether product regenerating
sulphuric acid.
Overall reaction
H2SO4
OH O

d) Phosphoric acid will react with the double bond to generate a tertiary carbocation.
The alcohol group in the molecule is the best nucleophile available and will react with the
carbocation.
The slightly basic dihydrogen phosphate ion will deprotonate the ether product, regenerating
phosphoric acid.
Overall reaction
H3PO4
O
OH
e) Sulphuric acid will protonate the double bond to form a resonance-stabilized carbocation,
which is more stable than the tertiary carbocation that could form.
The alcohol group will be the nucleophile reacting with the carbocation. Then, the hydrogen
sulphate will remove the hydrogen from the protonated intermediate, giving the final product.

There are stereochemical isomers possible in this product, since the hydrogens on the two
carbons shared by both rings can be cis or trans to each other. The two isomers are shown in
the overall reaction below.
Overall reaction
H H
O H2SO4 O O O O
OH
H H
cis trans
The reaction proceeds from reactant A through intermediates B and C to final product D, as
shown in the figure below.
OH2 OH
A B C D
B
Energy
C
A
Reaction progress
The product D is more stable than the reactant A, so it is represented with the lower energy. Both
intermediates are less stable than either A or D. Comparing B to C, B is shown at the highest
energy (least stable), since the only bonds are broken going from A ─> B, but an new C–O bond
is made going from B ─> C. This would make C significantly lower in energy than B.

a) The π bond will be the nucleophile and the mercury atom will be the electrophile in the first
step.
The second step will be the nucleophilic methanol reacting with the electrophilic carbon in
the mercurium ion. Either side leads to the same regioisomer (but not stereoisomers), so only
one pathway needs to be considered.
The only regioisomer will be
b) Mercuric acetate reacts to form a symmetric intermediate.
Only one regioisomer will form, since attack at either side of the mercurium ion results in
the same regioisomer.
The acetate ion will deprotonate the intermediate to form the final product.

c) The initial product is asymmetric, so regioisomers need to be considered.
There are two pathways from this intermediate, each leading to a different regioisomer.
Path A will be the favoured one, with the incoming nucleophile attacking the tertiary carbon,
which would have the greater carbocation character.
fast O
HgOAc
+ Hg(OAc) 2
major product
HO
O
slow
HgOAc
d) The initial product is asymmetric.

The two pathways the reaction can proceed through are outlined below as Path A and
Path B.
Path A
OAc H Me Me
O O
Me OH
HgOAc
HgOAc HgOAc
+ HOAc
Path B
Me OH
HgOAc HgOAc
HgOAc
O O
Me H Me
OAc + HOAc
In Path A, the methanol reacts with a primary carbon, while in Path B, the methanol reacts at
the secondary site. There will be more positive charge on the secondary site, so Path B will
be the preferred pathway.
slow
Me
O
HgOAc
+ Hg(OAc) 2
MeOH
fast HgOAc
O
Me
major product
The two products that result are stereoisomers. They are produced from the mercuric acetate
approaching from either side of the double bond. These are labelled Path A and Path B below.
The arrows are not meant to denote electron movement; rather, the approach of the mercuric

acetate to the double bond. Products A and B are mirror images of each other and are, therefore,
enantiomers of each other.
a) The bromonium ion formed has a tertiary carbon, which is the preferred site for the incoming
nucleophile. The nucleophile adds trans to the bromine leading to a trans product.
b) The initial ion has primary and secondary carbons at the reactive site. The secondary site will
react fastest and lead to the indicated product.
c)
d)

e)
f)
Reactions reversed to move from products to reactants.
a)
b)
c)
d)

a)
b)
c)
d)

This transformation could potentially be accomplished by using Cl2 and water. The
regiospecificity of the addition would give the desired product.
Epoxidation and ring opening with chloride could give the desired product. In order to get the
regiochemistry correct, the ring opening would have to be done in neutral conditions. This would
bring about preferred chloride attack at the primary carbon.
Any chiral molecules will be produced as racemic mixtures.
a)
b)
c)

d)
e)
a) Regioselective, stereospecific
b) Regioselective, stereospecific
c) Stereospecific
d) Stereoselective

a) Not conjugated, same as alkene reaction
b)
c)
d)

a) D
D G‡ D G‡
C,B C,D
B
Energy
Reaction coordinate
b) The kinetic product is formed fastest with the smallest energy barrier. The smallest barrier is
C → B (ΔG‡C,B), so A would be the kinetic product.
c) The thermodynamic product would be A, as it is the most stable.
d) B and D would be the transition states in this diagram.
a)
b)

c)
d)
a)
b)

PROBLEMS
8.21
The pair of electrons was being equally shared by the two carbon atoms. In the product, one
carbon is still sharing its electron in the carbon–electrophile bond (no change in charge). The
other carbon has lost the electron it used to be sharing, so it has a +1 charge. As well, charge
conservation still applies to organic reactions.
8.22
a)
b)
c)
d)
e)

8.23
The reverse reaction would be thermodynamically unfavourable, since the products in the
reverse reaction would be higher in energy than its reactants.
The rate-determining step would be the first step in the reverse reaction (second step in the
forward reaction), as it has the highest activation energy barrier.
reverse reaction direction
highest activation energy

for reverse reaction
Energy
+ Br
H
reverse reaction
is endothermic Br
+ H
Br
Reaction coordinate
8.24
The carbocation formed is the key to understanding this outcome. The diene is symmetric, so
reaction with HBr at either double bond gives the same initial carbocation. The incoming
bromide nucleophile can attack this resonance-stabilized carbocation at either site of partial
positive charge to form the two products.

8.25
Both products form from the same carbocation.
In one case, the carbocation reacts with water, acting as a nucleophile.
In the other case, water acts as a base to remove a proton.

8.26
a)
The carbocation circled above is the more stable because it is a tertiary carbocation, while
the other is a secondary carbocation. The more alkyl-substituted carbocation has more
stabilization through induction. It is formed faster because the inductive effects that make
this tertiary carbocation more stable also make the transition state that leads to its formation
more stable.
b)
Both carbocations are tertiary, but the oxygen containing one is resonance stabilized. This
resonance stabilization will be present, to some degree, in the transition state leading to this
intermediate. It will have a lower energy of activation and form faster.
The carbocation on the right will form from a transition state of higher energy since it is not
resonance stabilized. It will form more slowly.
c)
Both are secondary carbocations, but the indicated one also has resonance stabilization. The
resonance-stabilized intermediate will form faster, since the transition state leading to its
formation will be more stable due to resonance.

8.27
a)
b)
c) The alkene is symmetrical, so the two carbocation intermediates that form are
indistinguishable and of identical energy. The product of each is the same.
d)

8.28
In the reaction of a) with HBr, a centre of chirality is created. Both enantiomers will be formed in
equal amounts.
In the reaction of b) with HBr, one non-chiral product is formed from one of the possible
carbocations. Two other chiral products form through the other carbocation intermediate. In the
reaction of b) with HBr, the two carbocation intermediates formed will be of comparable
stabilities. An achiral product is formed from one of the carbocations. Two additional chiral
products are obtained from the other carbocation intermediate.

8.29
a) and b)
HBr Addition
H2O Addition
CH3CH2OH Addition
c) Acid is needed because water and alcohols are not acidic enough to protonate the alkene.
d) Yes. Thiol addition would require an acid catalyst because, though more acidic than an
alcohol or water, it is not acidic enough to protonate the alkene.

8.30
The oxymercuration/demercuration reaction takes place under milder reaction conditions than
those used in acid catalysed hydrolysis of alkenes. This is important if other parts of the organic
substrate are sensitive to such conditions. The reaction is irreversible, so higher product yields
can be obtained. Acid-catalyzed hydration occurs through carbocation intermediates, which may
rearrange (see Chapter 10), leading to more complex mixtures of products. Oxymercuration
/demercuration has no carbocation intermediate and, thus, usually avoids this complication.
8.31
The addition of a nucleophile to a three-membered ring usually proceeds with anti-

stereochemistry in order for the filled orbitals of the nucleophile to overlap with the empty *
orbital of the carbon-leaving group bond. In a three-membered ring, this means the nucleophile
must approach from the face of the ring opposite the leaving group.

8.32
a) It is neither stereoselective nor stereospecific. Since the carbocation intermediate is planar,

the nucleophile can approach from either face. The only selectivity comes if there is a
nearby chiral centre (especially if it is sterically bulky), which may make an approach from
one side of the carbocation easier than from the other. In this case the reaction would be
stereoselective.
b) These reactions are stereospecific, achieved by reaction of the alkene with Cl2 and H2O. The
intermediate is a bridged chloronium ion, so the incoming nucleophile must add anti-
periplanar to the carbon-chlorine bond that is being broken (see the preceding question). The
products will have the chlorine and hydroxyl groups trans to each other.
c) These reactions are stereospecific. The intermediate is a bridged bromonium ion, so the
incoming bromide must add anti-periplanar to the carbon-bromine bond (similar to part (b)).
The products will have bromines trans to each other.
d) The reaction is stereospecific. The H–B bond adds in a concerted fashion, with the new C–H
and C–B bonds forming at the same time on the same face of the alkene. The oxidative
removal of the boron does not affect the stereochemistry produced in the first step. This will
always give syn-addition products.
e) Hydrogenation on a metal surface is stereospecific. Both hydrogens are delivered to the

same face of the alkene when it approaches the surface of the catalyst; syn-addition.
f) Stereospecific. A concerted reaction forms both C–O bonds at the same time on the same
face of the alkene; syn-addition.

8.33
a) This is a formal addition of H2O to an alkene. The alkene would be
Either acid catalyzed addition of water (e.g. H2SO4(cat), H2O) or oxymercuration in water
(Hg(OAc)2, H2O) followed by a reductive removal of the mercury with NaBH4.
b) This is addition of water to an alkene. In order to get the –OH group on the carbon atom
indicated, that carbon must be the site of the most stable carbocation intermediate.
The reagents are similar to those of part (a): acid catalyzed addition of water (e.g.,
H2SO4(cat), H2O) or oxymercuration in water (Hg(OAc)2, H2O) followed by a reductive
removal of the mercury with NaBH4. Note that the oxymercuration is the preferred route, as
the acid catalyzed reaction may lead to a rearranged product.
c) The alkene must include the carbon to which the –OH has added, so the only possibility is
However, a Markovnikov addition to this would give the wrong product.
So, hydroboration followed by oxidation is needed (anti-Markovnikov addition).

d) Formation of this product would involve HCl addition. However, there are two possible
alkenes that could be considered.
Considering the possible products of each:
3-hexene leads only to the desired regioisomer, but 2-hexene produces two regioisomers.
3-hexene will be the better starting material.

e) There are two alkenes to consider. Using Cl2 as reagent, the two chlorine atoms will add
stereospecifically with a trans orientation.
The trans alkene does not give the correct stereochemistry.
The cis alkene does lead to the correct final product.

f) One way to get a mixture of diastereomers is to invert all but one of the chiral centres.
These two alkanes can be formed from the same alkene by addition of hydrogen across
different faces of the double bond.
8.34
The bond to make the ring was formed at the O atom. Taking this into consideration, there are
two possible starting materials.
To form the desired product, the initial carbocation formed by each alkene must be on the carbon indicated
Compound A will not work, as the stable carbocation would be on the secondary carbon, which
will cyclize to a four-membered ring, not the desired product.
Compound B would form the needed carbocation, leading to the following mechanism of formation.

8.35
a) The first step is hydrogenation, with a poisoned catalyst giving only a single reduction.
Then, the resulting alkene undergoes hydroboration.
Oxidative removal of the borane gives the final alcohol product.
b) In the second sequence, a sterically hindered borane would first add to the alkyne.
Then, oxidative removal of the borane group would lead to an intermediate enol, which
would rearrange into an aldehyde.
c) In the third sequence, the first step is hydration of one of the π bonds, forming an enol that
rearranges into the more stable ketone.
The second step uses borohydride to reduce the ketone to an alcohol.

8.36
a)
b)
8.37
a) This would be a simple Markovnikov addition of water to the double bond. So, either acid
catalyzed hydration or oxymercuration followed by reductive workup with sodium
borohydride will form the product.
b) This is a Markovnikov addition of methanol to the alkene. Using methanol with an acid
catalyst or oxymercuration in methanol followed by reduction would give the desired product.

c) The formation of this halohydrin requires bromine in water, since the water would add to the
initial bromonium ion to produce the regiochemistry required.
d) To form this halohydrin, the nucleophile used last will be the bromide. Formation of an
epoxide with mCPBA followed by bromide ion under acidic conditions gives the desired
regiochemistry.
e) This is anti-Markovnikov addition of water. So, a borane is needed to add the initial
hydrogen with this regiochemistry. The borane can be removed oxidatively to give the final
alcohol.
f) This is an epoxidation reaction with mCPBA.
g) The product is obtained by addition of HCl to the double bond.
h) This is a catalytic addition of hydrogen over palladium on carbon.

8.38
a) Both products arise from the initial tertiary (most stable) carbocation. Path A is nucleophilic
addition of the bromide to produce the alkyl bromide product. The regiochemistry is
controlled by the site of the most stable carbocation.
Path A
Br Br
H Br
Path B leads to the alkene product. This is where the bromide ion acts as a base to remove a
hydrogen adjacent to the carbocation.
Path B
H Br Br
H
H
b) The regioselectivity is controlled by the location of the most stable carbocation in the
intermediates in both steps.
Step 1
H Cl Cl
Cl
most stable
carbocation
Step 2
H Cl Cl
Cl Cl Cl Cl
most stable
carbocation

c) The initial step is addition of water to a  bond. The alcohol that forms at the site of the most
stable carbocation intermediate is part of an enol. This rearranges to the more stable ketone
form to give the final product.

d) The first step is regiospecific. The incoming borane is sterically bulky, so the boron atom has
to react at the least hindered end of the alkyne. This regiochemistry is also reinforced by the
transition state in this reaction having a partial positive charge on the carbon nearest the
incoming H atom. This is most favourable at the carbon best suited to stabilize carbocations;
that is, the most substituted one.
Step 1
induced dipole
cis-addition
d- B
d+
H
B
H d+
d-
The second step removes the boron to form an alcohol intermediate.
The alcohol is part of an enol, which then rearranges to the more stable carbonyl compound
under the basic conditions of the reaction.

8.39
a) The first step in the reaction is analogous to addition of Br2 to an alkene.
In the next step, the fluoride ion acts as a nucleophile to open the bromonium ion. The
stereochemistry of the fluoride addition is controlled by two factors. First, F− adds trans to
the bromine atom. Second, F− adds to the most-substituted carbon, which will have the most
carbocation character.
trans addition F
F
Br
Br
most substituted
one enantiomer
Since the initial bromonium ion is a racemic mixture of enantiomers, so must be the
products, one of which is shown above.
b) The product shown in part (a) redrawn in chair conformation:
c) The product in part (b) flipped to the other chair conformation:
d) The configurations are assigned as shown below.

8.40
a) Since a specific stereochemistry is needed in the products, a stereospecific addition is likely

needed. The last step could be addition of Br2 to an alkene.
Br atoms are both trans

Br atoms are both cis
H Br H Br
Br Br H H Br H H
Br Br
Br H Br Br H
(2S, 3S) (2R, 3R)
2,3-dibromobutane (2S, 3S) (2R, 3R)
In rotating around the C–C bond to arrange the Br atoms in a trans fashion, it can be seen
that a cis-alkene would be needed to get the required stereochemistry from the trans addition
of Br2. A cis alkene is easily synthesized using an alkyne and Lindlar catalyst, since the
hydrogen adds with cis stereochemistry.
The reaction sequence would be
b) To add three halogens to a triple bond, a hydrohalogenation step and a halogenation step are
required. There is no stereochemistry to consider, so Cl2 addition followed by a HBr
addition would give the desired product.

c) The ketone is the result of the rearrangement of an enol.
The enol would be produced by oxymercuration-demercuration of the terminal alkyne.

Using the internal alkyne would create a mixture of regioisomers.
d) This product is a rearrangement of an enol intermediate.
The required alkyne would be the same as in part (c), but an anti-Markovnikov addition is
needed. This can be accomplished by hydroboration with a bulky borane.
H
H
BCy2 H H 2O 2
OH
H NaOH H
H BCy2
enol rearranges to
cis addition final aldehyde product
8.41
The bromine can add to a C–C double bond. The enol-keto equilibrium is the source of the C–C
double bond. A bromonium ion is the product of the first step.
The nearby lone pairs on the –OH group can act as an internal nucleophile, opening up the
bromonium ring. The protonated ketone is then deprotonated by the bromide ion acting as a base.

8.42
The first step in the reaction of nerol is an acid-catalyzed cyclization and loss of water.
From here, there are two pathways to form the products observed. The water present can act as a
base to remove a hydrogen and form an alkene, shown as Path 1 below.
Path 1
H2O
+ H 3O
H
H
H
The other pathway is the water acting as a nucleophile and attacking the carbocation to
ultimately form the alcohol product, shown as Path 2.
Path 2
+ H3O
H2O
O OH
H H
H2O
The reaction of geraniol is slightly different. The geometry of the double bond nearest the
alcohol group is opposite to that of the six-membered ring that forms. The isomerization can
occur by first forming an allyl carbocation.

This intermediate is resonance stabilized. However, the C–C bond can rotate into the geometry
found in nerol.
C–C bond
rotation
This geometry allows the formation of the six-membered ring by nucleophilic attack of the
double bond electrons on the terminal carbocation, forming a bond between the carbon atoms
labelled 1 and 2 below.
This is the same intermediate as formed in the nerol reaction and would follow Path 1 and Path 2
shown above to form the same final alkene and alcohol products.
MCAT Style Problems
8.43
Answer: (a). The first step determines the reaction rate, since the addition of the bromine creates
a bromonium intermediate of high energy.
8.44
Answer: (c). The carbon has three bonds, so it is considered sp2 hybridized.

8.45
Add the chlorine atoms trans to each other, then rotate into the conformation shown.
8.46
The regiochemistry of the reaction puts the –OH group on the more substituted carbon, so A and
B are not major products. The stereochemistry means C is the only possible major product
shown.

Challenge Problem
8.47
The –OH group is acting as a nucleophile. The first step is carbocation formation by adding a
proton to the alkene. The –OH group then reacts at the tertiary carbocation, forming a bicyclic
ring system. The chloride ion then deprotonates the intermediate to make the final product.

Another random document with
no related content on Scribd:
the 26th April, at noon, accompanied by his aide-de-camp,
Captain del Pilar, and Mr. Leyba, his private secretary. …
"Throughout the whole stay of General Aguinaldo in Singapore

the editor was kept fully informed daily of the progress of
affairs. Naturally, however, all statement of what occurred
has been withheld by us until what has been deemed the fitting
moment has arrived. The substance of the whole incident in its
relations to the recent course of affairs in the Philippines
has been very fully telegraphed by the editor both to New York
and London."
{594}
Mr. Pratt, the U. S. Consul-General at Singapore, had already,

under date of April 28, given his own official report of the
interview with General Aguinaldo, to the Department at
Washington, as follows:
"I have the honor to report that I sent you on the 27th
instant, and confirmed in my dispatch Number 211 of that date,
a telegram which deciphered read as follows. … 'General
Aguinaldo gone my instance Hongkong arrange with Dewey
co-operation insurgents Manila.
PRATT.'
"The facts are these: On the evening of Saturday the 23d

instant, I was confidentially informed of the arrival here,
incognito, of the supreme leader of the Philippine insurgents,
General Emilio Aguinaldo, by Mr. H. W. Bray, an English gentleman
of high standing, who, after fifteen years' residence as a
merchant and planter in the Philippines, had been compelled by
the disturbed condition of things resulting from Spanish
misrule to abandon his property and leave there, and from whom
I had previously obtained much valuable information for
Commodore Dewey regarding fortifications, coal deposits, etc.,
at different points in the islands. Being aware of the great
prestige of General Aguinaldo with the insurgents, and that no
one, either at home or abroad, could exert over them the same
influence and control that he could, I determined at once to
see him, and, at my request, a secret interview was
accordingly arranged for the following morning, Sunday, the
24th, in which, besides General Aguinaldo, were only present
the General's trusted advisers and Mr. Bray, who acted as
interpreter.
"At this interview, after learning from General Aguinaldo the

state of and object sought to be obtained by the present
insurrectionary movement, which, though absent from the
Philippines, he was still directing, I took it upon myself,
whilst explaining that I had no authority to speak for the
Government, to point out the danger of continuing independent
action at this stage; and, having convinced him of the
expediency of co-operating with our fleet, then at Hongkong,
and obtained the assurance of his willingness to proceed
thither and confer with Commodore Dewey to that end, should
the latter so desire, I telegraphed the Commodore the same day
as follows, through our consul-general at Hongkong:
'Aguinaldo, insurgent leader, here. Will come Hongkong arrange
with Commodore for general cooperation insurgents Manila if
desired. Telegraph.
PRATT.'
"The Commodore's reply reading thus:

'Tell Aguinaldo come soon as possible.
DEWEY.'
"I received it late that night, and at once communicated to

General Aguinaldo, who, with his aide-de-camp and private
secretary, all under assumed names, I succeeded in getting off
by the British steamer 'Malacca,' which left here on Tuesday,
the 26th. Just previous to his departure, I had a second and
last interview with General Aguinaldo, the particulars of
which I shall give you by next mail. The general impressed me
as a man of intelligence, ability, and courage, and worthy the
confidence that had been placed in him.
"I think that in arranging for his direct cooperation with

the commander of our forces, I have prevented possible
conflict of action and facilitated the work of occupying and
administering the Philippines. If this course of mine meets
with the Government's approval, as I trust it may, I shall be
fully satisfied; to Mr. Bray, however, I consider there is due
some special recognition for most valuable services rendered.
How that recognition can best be made I leave to you to
decide."
Two days later (April 30), Mr. Pratt reported further, as

follows: "Referring to my dispatch No. 212, of the 28th
instant, I have the honor to report that in the second and
last interview I had with General Emilio Aguinaldo, on the eve
of his departure for Hongkong, I enjoined upon him the
necessity, under Commodore Dewey's direction, of exerting
absolute control over his forces in the Philippines, as no
excesses on their part would be tolerated by the American
Government, the President having declared that the present
hostilities with Spain were to be carried on in strict accord
with modern principles of civilized warfare. To this General
Aguinaldo fully assented, assuring me that he intended and was
perfectly able, once on the field, to hold his followers, the
insurgents, in check and lead them as our commander should
direct. The general further stated that he hoped the United
States would assume protection of the Philippines for at least
long enough to allow the inhabitants to establish a government
of their own, in the organization of which he would desire
American advise and assistance. These questions I told him I
had no authority to discuss."
Of the arrival of Aguinaldo at Hongkong and his conveyance

thence to Manila, the following account was given by Mr.
Wildman, the U. S. Consul at Hongkong, in a communication to
the State Department at Washington, which bears date July 18:
"On May 2 Aguinaldo arrived in Hongkong and immediately called
on me. It was May 16 before I could obtain permission from
Admiral Dewey to allow Aguinaldo to go by the United States
ship 'McCulloch,' and I put him aboard in the night so as to
save any complications with the local Government. Immediately
on the arrival of Aguinaldo at Cavite he issued a
proclamation, which I had outlined for him before he left,
forbidding pillage, and making it a criminal offense to
maltreat neutrals. He, of course, organized a government of
which he was dictator, an absolutely necessary step if he
hoped to maintain control over the natives, and from that date
until the present time he has been uninterruptedly successful
in the field and dignified and just as the head of his
government. According to his own statements to me by letter,
he has been approached by both the Spaniards and the Germans,
and has had tempting offers made him by the Catholic Church.
He has been watched very closely by Admiral Dewey, Consul
Williams, and his own junta here in Hongkong, and nothing of
moment has occurred which would lead anyone to believe that he
was not carrying out to the letter the promises made to me in
this consulate. The insurgents are fighting for freedom from
the Spanish rule, and rely upon the well-known sense of
justice that controls all the actions of our Government as to
their future."
{595}
In reply to Consul Pratt's report of his interviews with

General Aguinaldo, and of his proceedings in connection with
the departure of that personage from Singapore to Hongkong,
the United States Secretary of State, Mr. Day, wrote, June 16,
as follows: "The Department observes that you informed General
Aguinaldo that you had no authority to speak for the United
States; and, in the absence of the fuller report which you
promise, it is assumed that you did not attempt to commit this
Government to any alliance with the Philippine insurgents. To
obtain the unconditional personal assistance of General
Aguinaldo in the expedition to Manila was proper, if in so
doing he was not induced to form hopes which it might not be
practicable to gratify. This Government has known the
Philippine insurgents only as discontented and rebellious
subjects of Spain, and is not acquainted with their purposes.
While their contest with that power has been a matter of
public notoriety, they have neither asked nor received from
this Government any recognition. The United States, in
entering upon the occupation of the islands, as the result of
its military operations in that quarter, will do so in the
exercise of the rights which the state of war confers, and
will expect from the inhabitants, without regard to their
former attitude toward the Spanish Government, that obedience
which will be lawfully due from them. If, in the course of
your conferences with General Aguinaldo, you acted upon the
assumption that this government would cooperate with him for
the furtherance of any plan of his own, or that, in accepting
his cooperation, it would consider itself pledged to recognize
any political claims which he may put forward, your action was
unauthorized and cannot be approved."
Treaty of Peace, and Accompanying Papers

(55th Congress, 3d Session, Senate Document Number 62,
part 2, pages 337-354).
See, also (in this volume),

PHILIPPINE ISLANDS: A. D. 1806-1808.
UNITED STATES OF AMERICA: A. D. 1898 (April-June).

The War with Spain.
Movements or the Spanish squadron under Admiral Cervera,
and the blockading of it in the harbor of Santiago de Cuba.
Lieutenant Hobson's exploit.
The sinking of the collier "Merrimac" in the channel.
The opening of hostilities found a Spanish squadron of four

armored cruisers (the "Cristobal Colon," the "Almirante
Oquendo," the "Vizcaya," and the "Infanta Maria Teresa,") with
three torpedo-boat destroyers (the "Pluton," "Furor" and
"Terror") and some lighter craft, assembled at the Cape Verde
islands, under Rear-Admiral Pascual Cervera. They were in
Portuguese waters, and Portugal, though friendly to Spain, was
forced to issue a proclamation of neutrality, on the 20th of
April, which required the Spanish fleet to depart. Some of the
vessels then returned to Spain; but the seven named above
sailed westward, and their destination became a mystery, very
exciting for some time to the American mind. They might
attempt to surprise some American coast city; they might
intercept the battle-ship "Oregon," then making her way from
the Pacific coast, by the long circuit around Cape Horn; they
might have some plan for breaking the Cuban blockade. Acting
on the latter conjecture, and surmising that Porto Rico would
be chosen for the Spanish naval base, Admiral Sampson moved in
that direction to seek them. He attacked the forts at San Juan
(May 12), and satisfied himself that no fleet was in the bay.
The truth was that Cervera was then just entering the
Caribbean Sea, considerably to the south of Sampson's search.
He touched at the French island of Martinique, and at the
Dutch island of Curaçoa, and then slipped across to Santiago
de Cuba, where he was to be overtaken by his fate. In the long
hill-sheltered bay, with a narrow entrance, which forms this
excellent Cuban harbor, the Spanish fleet was so hidden that
nearly a fortnight passed before its whereabouts could be
fully ascertained. It was not until May 20 that a blockade of
Santiago was established by a flying squadron of the American
fleet, under Commodore Schley, with certainty that the
squadron of Cervera was harbored there. On the 1st of June,
Admiral Sampson arrived on the scene, with a stronger naval
force, and took command. To attempt to force the narrow
entrance of the harbor, strongly fortified and thickly mined
as it was, and attack the Spanish fleet in the bay, was not
deemed practicable. The course resolved upon was to hold the
enemy fast in the shelter he had sought, until Santiago could
be taken, by a land attack. In pursuance of this plan, an
exploit of splendid daring was performed, in the early morning
of June 3, by a young officer, Lieutenant Richmond Pearson
Hobson, with a crew of seven volunteers, who placed and sank a
huge coaling ship, the "Merrimac," in the channel that leads
into Santiago Bay. The following is Admiral Sampson's report
of the undertaking and its achievement:
"Before coming here, I decided to make the harbor entrance

secure against the possibility of egress of the Spanish ships
by obstructing the narrow part of the entrance by sinking a
collier at that point. Upon calling upon Mr. Hobson for his
professional opinion as to a sure method of sinking the ship,
he manifested a most lively interest in the problem. After
several days' consideration he presented a solution which he
considered would insure the immediate sinking of the ship when
she had reached the desired point in the channel. This plan we
prepared for before we reached Santiago. This plan included
ten electric torpedoes on the outside of the ship, each of 78
pounds of gunpowder, sinking the ship partially before going
in, cutting the sea valves, and opening the cargo ports. The
plan contemplated a crew of only seven men and Mr. Hobson, who
begged that it might be intrusted to him. The anchor chains
were ranged upon deck for both the anchors, forward and aft,
the plan including the anchoring of the ship almost
automatically. As soon as I reached Santiago and had the
collier to work upon the details were commenced and diligently
prosecuted, hoping to complete them in one day, as the moon
and tide served best the first night after our arrival.
Notwithstanding every effort, the hour of 4 o'clock in the
morning arrived and the preparations were scarcely completed.
After a careful inspection of the final preparations I was
forced to relinquish the plan for that morning, as dawn was
breaking. Mr. Hobson begged to try it at all hazards.
"This morning proved more propitious, as a prompt start could

be made. Nothing could have been more gallantly executed. We
waited impatiently after the firing by the Spaniards had
ceased. When they did not reappear from the harbor at 6
o'clock I feared they had all perished. A steam launch, which
had been sent in charge of Naval Cadet Powell to rescue the
men, appeared at this time, coming out under a persistent fire
from the batteries, but brought none of the crew. A careful
inspection of the harbor from this ship showed that the
'Merrimac' had been sunk in the channel somewhat farther in
than had been intended.
{596}
This afternoon the chief of staff of Admiral Cervera came out
under a flag of truce with a letter from the Admiral extolling
the bravery of the crew in an unusual manner. I can not myself
too earnestly express my appreciation of the conduct of Mr.
Hobson and his gallant crew. I venture to say that a more
brave and daring thing has not been done since Cushing blew up
the 'Albemarle.'" The sunken ship did not actually block the
channel; but that fact takes nothing from the gallantry of the
exploit. Why the intended spot in the channel was missed was
explained by Lieutenant Hobson in a statement which he
afterwards made: "When the 'Merrimac' poked her nose into the
channel," says the Lieutenant, "our troubles commenced. The
deadly silence was broken by the swash of a small boat
approaching us from the shore. I made her out to be a picket
boat. She ran close up under the stern of the 'Merrimac' and
fired several shots from what seemed to be 3 pounder guns. The
'Merrimac's' rudder was carried away by this fire. That is why
the collier was not sunk across the channel. We did not discover
the loss of the rudder until Murphy [the volunteer assigned to
that duty] had cast anchor. We then found that the 'Merrimac'
would not answer to the helm and were compelled to make the
best of the situation. … Submarine mines and torpedoes were
exploded all around us, adding to the excitement. The mines
did no damage, although we could hear the rumbling and feel
the ship tremble. We were running without lights, and only the
darkness saved us from utter destruction. When the ship was in
the desired position and we found that the rudder was gone, I
called the men on deck. While they were launching the
catamaran I touched off the explosives. At the same time two
torpedoes, fired by the 'Reina Mercedes,' struck the
'Merrimac' amidships. I can not say whether our own explosives
or the Spanish torpedoes did the work, but the 'Merrimac' was
lifted out of the water, and almost rent asunder."
What followed, in the experience of the crew, when their

vessel went down, is described as follows by Lieutenant
Hobson, in a narrative of "The Sinking of the Merrimac," which
he published at a later day: "The stricken vessel now reeled
to port. Some one said: 'She is going to turn over on us,
sir,' to which I replied: 'No; she will right herself in
sinking, and we shall be the last spot to go under.' The
firing suddenly ceased. The vessel lowered her head like a
faithful animal, proudly aware of its sacrifice, bowed below
the surface, and plunged forward. The stern rose and heeled
heavily; it stood for a moment, shuddering, then started
downward, righting as it went. A great rush of water came up
the gangway, seething and gurgling out of the deck. The mass
was whirling from right to left 'against the sun'; it seized
us and threw us against the bulwarks, then over the rail. Two
were swept forward as if by a momentary recession, and one was
carried down into a coal-bunker—luckless Kelly. In a moment,
however, with increased force, the water shot him up out of
the same hole and swept him among us. The bulwarks
disappeared. A sweeping vortex whirled above. We charged about
with casks, cans, and spars, the incomplete stripping having
left quantities on the deck. The life-preservers stood us in
good stead, preventing chests from being crushed, as well as
buoying us on the surface; for spars came end on like
battering-rams, and the sharp corners of tin cans struck us
heavily. … When we looked for the life-boat we found that it
had been carried away. The catamaran was the largest piece of
floating debris; we assembled about it. The line suspending it
from the cargo-boom held and anchored us to the ship, though
barely long enough to reach the surface, causing the raft to
turn over and set us scrambling as the line came taut.
"The firing had ceased. It was evident the enemy had not seen
us in the general mass of moving objects; but soon the tide
began to drift these away, and we were being left alone with
the catamaran. The men were directed to cling close in, bodies
below and only heads out, close under the edges, and were
directed not to speak above a whisper, for the destroyer was
near at hand, and boats were passing near. We mustered; all
were present, and direction was given to remain as we were
till further orders, for I was sure that in due time after
daylight a responsible officer would come out to reconnoiter.
It was evident that we could not swim against the tide to
reach the entrance. Moreover, the shores were lined with
troops, and the small boats were looking for victims that
might escape from the vessel. The only chance lay in remaining
undiscovered until the coming of the reconnoitering boat, to
which, perhaps, we might surrender without being fired on. …
The air was chilly and the water positively cold. In less than
five minutes our teeth were chattering; so loud, indeed, did
they chatter that it seemed the destroyer or the boats would
hear. … We remained there probably an hour."
At daylight a steam launch approached, and was hailed by

Lieutenant Hobson, who judged that there must be officers on
board to whom it would be safe to surrender. He was more than
right. The commander of the launch was Admiral Cervera, in
person, who took the nearly exhausted men from the water and
treated them with great kindness, admiring the bravery of
their exploit, and sending a flag of truce to Admiral Sampson
to announce their safety. They were taken aboard the 'Reina
Mercedes,' and, as prisoners of war, were confined at first in
Morro Castle, and afterwards in the city. It so happened that
they were locked in the Morro during a bombardment of the
Spanish coast defences and fleet by ten of our vessels on June
6th, when about 1,500 projectiles were fired; and much anxiety
and indignation were expressed in this country in view of that
circumstance; but Mr. Ramsden, British consul at Santiago,
explained in a despatch that they were removed as soon as
lodgings could be prepared in the barracks—actually on June
7th. They were released on July 6th in exchange for prisoners
captured by our forces.
{597}
UNITED STATES OF AMERICA: A. D. 1898 (April-July).

War with Spain,
Destruction of the Spanish fleet in Manila Bay.
Despatches of Admiral Dewey.
His relations with Aguinaldo, the insurgent chief.
Arrival of American troops for the occupation of the city.
Commodore George Dewey, commanding the Asiatic Squadron, then

awaiting orders at Hongkong, received on the 25th of April the
following despatch by cable from the Secretary of the Navy: "War
has commenced between the United States and Spain. Proceed at
once to Philippine Islands. Commence operations at once,
particularly against the Spanish fleet. You must capture
vessels or destroy. Use utmost endeavors." On the sixth day
after receiving these orders (namely on May 1st), he was able
to report from Manila, by a telegram sent from Hongkong on the
7th: "The squadron arrived at Manila at daybreak this morning.
Immediately engaged enemy and destroyed the following Spanish
vessels: 'Reina Christina,' 'Castillia,' 'Don Antonio de
Biloa,' 'Don Juan de Austria,' 'Isla de Luzon,' 'Isla de
Cuba,' 'General Lezo,' 'Marques del Duaro,' 'El Curreo,'
'Velasco,' one transport, 'Isla de Mandano,' water battery at
Cavite. I shall destroy Cavite arsenal dispensatory. The
squadron is uninjured. Few men were slightly wounded. I
request the Department will send immediately from San
Francisco fast steamer with ammunition. The only means of
telegraphing is to the American consul at Hongkong."
In due time the post brought particulars of the action, in the
following report from Commodore Dewey, dated May 4: "The
squadron left Mirs Bay, [China] on April 27, immediately on
the arrival of Mr. O. F. Williams, United States consul at
Manila, who brought important information and who accompanies
the squadron. Arrived off Bolinao on the morning of April 30
and, finding no vessels there, proceeded down the coast and
arrived off the entrance to Manila Bay on the same afternoon.
The 'Boston' and 'Concord' were sent to reconnoiter Port
Subic, I having been informed that the enemy intended to take
position there. A thorough search of the port was made by the
'Boston' and 'Concord,' but the Spanish fleet was not found,
although, from a letter afterwards found in the arsenal (
inclosed with translation), it appears that it had been their
intention to go there. Entered the Boca Grande, or south
channel, at 11.30 p. m., steaming in column at distance at 8
knots. After half the squadron had passed, a battery on the
south side of the channel opened fire, none of the shots
taking effect. The 'Boston' and 'McCulloch' returned the fire.
The squadron proceeded across the bay at slow speed, and
arrived off Manila at daybreak, and was fired upon at 5.15 a.
m. by three batteries at Manila and two at Cavite and by the
Spanish fleet anchored in an approximately east and west line
across the mouth of Bakor Bay, with their left in shoal water
in Canacao Bay. The squadron then proceeded to the attack, the
flagship 'Olympia,' under my personal direction, leading,
followed at distance by the 'Baltimore,' 'Raleigh,' 'Petrel,'
'Concord,' and 'Boston,' in the order named, which formation
was maintained throughout the action. The squadron opened fire
at 5.41 a. m. While advancing to the attack, two mines were
exploded ahead of the flagship, too far to be effective. The
squadron maintained a continuous and precise fire at ranges
varying from 5,000 to 2,000 yards, countermarching in a line
approximately parallel to that of the Spanish fleet. The
enemy's fire was vigorous, but generally ineffective.
"Early in the engagement two launches put out toward the

'Olympia' with the apparent intention of using torpedoes. One
was sunk and the other disabled by our fire and beached before
an opportunity occurred to fire torpedoes. At 7 a. m. the Spanish
flagship 'Reina Christina' made a desperate attempt to leave
the line and come out to engage at short range, but was
received with such galling fire, the entire battery of the
'Olympia' being concentrated upon her, that she was barely
able to return to the shelter of the point. The fires started
in her by our shell at this time were not extinguished until
she sank. At 7.35 a. m., it having been erroneously reported
to me that only 15 rounds per gun remained for the 5-inch
rapid-fire battery, I ceased firing and withdrew the squadron
for consultation and a redistribution of ammunition, if
necessary. The three batteries at Manila had kept up a
continuous fire from the beginning of the engagement, which
fire was not returned by this squadron. The first of these
batteries was situated on the south mole head at the entrance
to the Pasig River, the second on the south bastion of the
walled city of Manila, and the third at Malate, about one-ha]f
mile farther south. At this point I sent a message to the
Governor-General to the effect that if the batteries did not
cease firing the city would be shelled. This had the effect of
silencing them.
"At 11.16 a. m., finding that the report of scarcity of

ammunition was incorrect, I returned with the squadron to the
attack. By this time the flagship and almost the entire
Spanish fleet were in flames, and at 12.30 p. m. the squadron
ceased firing, the batteries being silenced and the ships
sunk, burnt, and deserted. At 12.40 p. m. the squadron
returned and anchored off Manila, the 'Petrel' being left
behind to complete the destruction of the smaller gunboats,
which were behind the point of Cavite. This duty was performed
by Commander E. P. Wood in the most expeditious and complete
manner possible. The Spanish lost the following vessels:
Sunk—'Reina Christina,' 'Castillia,' 'Don Antonio de Ulloa.'
Burnt—'Don Juan de Austria,' 'Isla de Luzon,' 'Isla de Cuba,'
'General Lezo,' 'Marques del Duaro,' 'El Correo,' 'Velasco,'
and 'Isla Mindanao,' (transport). Captured—'Rapido,' and
'Hercules' (tugs), and several small launches. I am unable to
obtain complete accounts of the enemy's killed and wounded,
but believe their loss to be very heavy. The 'Reina Christina'
alone had 150 killed, including the captain, and 90 wounded.
"I am happy to report that the damage done to the squadron

under my command was inconsiderable. There were none killed,
and only 7 men in the squadron very slightly wounded. As will
be seen by the reports of the commanding officers which are
herewith inclosed, several of the vessels were struck and even
penetrated, but the damage was of the slightest, and the
squadron is in as good condition now as before the battle. I
beg to state to the Department that I doubt if any commander
in chief, under similar circumstances, was ever served by more
loyal, efficient, and gallant captains than those of the
squadron now under my command. … On May 2, the day following
the engagement, the squadron again went to Cavite, where it
remains. A landing party was sent to destroy the guns and
magazines of the batteries there. … On the 3d the military
forces evacuated the Cavite Arsenal, which was taken
possession of by a landing party."
{598}
Promptly in response to this report of his victory, a joint

resolution of thanks to Commodore Dewey and his officers and
men, by the two Houses of Congress, was despatched to them,
with announcement to the former of his promotion to the rank
of rear-admiral. The admiral replied, on the 13th, from
Cavite, making due acknowledgments, and adding: "I am
maintaining strict blockade of Manila by sea, and believe
rebels are hemming in by land, although they are inactive and
making no demonstrations. Great scarcity of provisions in the
city. I believe the Spanish Governor-General will be obliged
to surrender soon. I can take Manila at any moment. To retain
possession and thus control Philippine Islands would require,
in my best judgment, a well equipped force of 5,000 men."
On the 20th he reported, further: "Aguinaldo, the rebel

commander in chief, was brought down by the 'McCulloch' [from
Hongkong]. Organizing forces near Cavite and may render
assistance that will be valuable." On the 27th of June, in
reply to inquiries from the Navy Department, he explained his
relations with Aguinaldo, as follows: "Aguinaldo, insurgent
leader, with thirteen of his staff, arrived May 19, by
permission, on 'Nanshan.' Established self Cavite, outside
arsenal, under the protection of our guns, and organized his
army. I have had several conferences with him, generally of a
personal nature. Consistently I have refrained from assisting
him in any way with the force under my command, and on several
occasions I have declined requests that I should do so,
telling him the squadron could not act until the arrival of
the United States troops. At the same time I have given him to
understand that I consider insurgents as friends, being
opposed to a common enemy. He has gone to attend a meeting of
insurgent leaders for the purpose of forming a civil
government. Aguinaldo has acted independently of the squadron,
but has kept me advised of his progress, which has been
wonderful. I have allowed to pass by water recruits, arms, and
ammunition, and to take such Spanish arms and ammunition from
the arsenal as he needed. Have advised frequently to conduct
the war humanely, which he has done invariably. My relations
with him are cordial, but I am not in his confidence. The
United States has not been bound in any way to assist
insurgents by any act or promises, and he is not, to my
knowledge, committed to assist us. I believe he expects to
capture Manila without my assistance, but doubt ability, they
not yet having many guns. In my opinion these people are far
superior in their intelligence and more capable of
self-government than the natives of Cuba, and I am familiar
with both races."
Report of the Secretary of the Navy, 1898,
volume 2, pages 67-72 and 103.
On the 30th of June, troops sent from San Francisco, to the

number of 2,500 officers and men, commanded by General T. M.
Anderson, arrived in Manila Bay, to co-operate with the navy
in taking Manila and occupying the city, when taken. They were
followed by a second expeditionary force, under General F. V.
Greene, which arrived July 17, and by a third, July 25 and 31,
with which came General Merritt, commanding the corps and the
Department of the Pacific. General Merritt's army then
numbered nearly 11,000 men, and it was increased during the
next few weeks to more than 15,000.
Reports of the War Department, 1898,

volume 1, part 2, page 499.
An English officer, Major Younghusband, who visited Manila at

this time, remarked: "It may, perhaps, with some confidence be
prophesied that when the cold fit, which will in due course
follow the warmth of the present enthusiasm, falls on the
nation, America will discover that the true parting of the
ways was … in having allowed Admiral Dewey to do more than
defeat the Spanish fleet and exact a heavy indemnity from the
city of Manila before sailing away." It would seem to be more
true, however, to say that the parting of the ways was when a
military expedition was sent from San Francisco to Manila, to
be landed, for the capture of the city and for the occupation
of the islands. It is claimed with reason that Admiral Dewey
could not "sail away," after the destruction of the Spanish
ships, because he needed the harbor he had seized, his fleet
having lost most of the privileges it had formerly been using
in neutral ports, when it became the fleet of a belligerent
power. To retain possession of Manila Bay while it was needed
by the American fleet was clearly a measure connected
legitimately with the general conduct of the war against
Spain. But it is difficult to see that the landing of soldiers
on the island of Luzon and the capture of the city of Manila
added anything to the security with which the Bay was held for
the purposes of Admiral Dewey's fleet, or that it contributed
at all to the weakening of Spain in the war, and to the rescue
of Cuba from Spanish misrule. For two months, from the first
day of May until the last day of June, before a soldier
arrived, and for six weeks longer, before Manila surrendered,
Admiral Dewey appears to have been as fully and as
conveniently in possession of all the advantages that
harborage there could give him, as he was after the Spanish
flag had been lowered in the city and on the island.
Therefore, the American conquest of the Philippines does not
readily connect itself with the war for the liberation of
Cuba, as a necessary part of it, but presents itself to the
mind as a somewhat supplementary enterprise, undertaken with
objects of its own.
UNITED STATES OF AMERICA: A. D. 1898 (May-August).

Conduct of English and German naval officers at Manila.
While Admiral Dewey was holding Manila Bay, before the taking
of the city, there were many rumors and exciting stories
afloat, of offensive behavior towards the American fleet by
commanders of German war ships that were sent to the scene. As
far as possible, the facts were officially suppressed, in
order to avoid a quarrel between the two countries, and no
authoritative account of what occurred can be found. But some
incidents obtained publicity which are probably true in the
main. The first unpleasant happening appears to have been the
arrival in Manila Bay of a German naval vessel, which steamed
in with entire disregard of the blockading fleet, as though
the port was its own. Thereupon Admiral Dewey sent a forcible
reminder to the captain that he was intruding upon a blockade,
by firing a shot across his bow, and ordering him to heave to.
The German captain, in a rage, is said to have called on the
commanding officer of a British squadron that was in the Bay,
for advice as to what he should do, and was told that he owed
the American Admiral an apology for his violation of naval
etiquette, well settled for such circumstances as those
existing in Manila Bay. According to the story, the British
commander, Captain Sir Edward Chichester, himself on the best
of terms with Admiral Dewey, visited the latter, on behalf of
the German officer, and made the matter smooth.
{599}
But, either through indiscretion of his own, or because he had
instructions to interfere as much as possible with the
proceedings of the Americans, the German commander continued
to pursue an offensive course. According to report, be went so
far as to stop a movement which Aguinaldo (then a recognized
ally of the United States) was making, to take possession of a
certain island, and to capture some Spaniards who were on it.
This provoked Admiral Dewey to a demonstration against him so
threatening that he drew back in haste, and the island was
occupied.
According to all accounts, Admiral Dewey showed unsurpassed

wisdom and dignity in meeting and checking these offensive
proceedings without allowing them to become a cause of
international quarrel; and he was happily aided in doing so by
the hearty support of the British naval commander. According
to still another report of the time, a German admiral, who had
come upon the scene, meditated an interference to forbid the
bombarding of Manila, when the city was about to be attacked,
and, calling upon Sir Edward Chichester to ascertain what
action the latter would take, was significantly told, "That is
only known to Admiral Dewey and myself,"—which convinced him
that his project was not wise. An English writer has related,
with much satisfaction, that when Sir Edward's ship, the
"Immortalité," finally steamed out of Manila Bay, returning to
Hong Kong, "every ship in the American fleet manned her yards
and gave the British man-of-war three cheers as she passed
along; and she with the answering signal, 'thank you,' flying
at her mast-head, went on her way."
UNITED STATES OF AMERICA: A. D. 1898 (June).
Act creating the United States Industrial Commission.
An Act "authorizing the appointment of a non-partisan

Commission to collate information and to consider and
recommend legislation to meet the problems presented by labor,
agriculture, and capital," was passed by Congress and approved
by the President June 18, 1898. It provided:
"That a commission is hereby created, to be called the

'Industrial Commission,' to be composed as follows. Five
members of the Senate, to be appointed by the presiding
officer thereof; five members of the House of Representatives,
to be appointed by the Speaker, and nine other persons, who shall
fairly represent the different industries and employments, to
be appointed by the President, by and with the advice and
consent of the Senate. … That it shall be the duty of this
commission to investigate questions pertaining to immigration,
to labor, to agriculture, to manufacturing, and to business,
and to report to Congress and to suggest such legislation as
it may deem best upon these subjects. … That it shall furnish
such information and suggest such laws as may be made a basis
for uniform legislation by the various States of the Union, in
order to harmonize conflicting interests and to be equitable
to the laborer, the employer, the producer, and the consumer.
… That the commission shall give reasonable time for hearings,
if deemed necessary, and if necessary it may appoint a
subcommission or subcommissions of its own members to make
investigation in any part of the United States, and it shall
be allowed actual necessary expenses for the same. It shall
have the authority to send for persons and papers and to
administer oaths and affirmations. … That it may report from
time to time to the Congress of the United States, and shall
at the conclusion of its labors submit a final report."
The Commission thus contemplated was duly appointed by the

President, and organized by the election of Senator Kyle for
its chairman. For the scope and plan of its investigations a
committee on procedure made the following recommendations,
which were adopted by the Commission and which have been
followed in what it has done:
"The main work of the Commission may … be said to be to study

and compare existing laws bearing upon industrial conditions,
here and elsewhere, to ascertain by competent testimony
wherein they are deficient, defective, inoperative, or
oppressive, and to recommend such remedial statutes as will
tend not only to make the conditions of industry more uniform
as between the several States, but to remove such existing
sources or causes of discontent, inequality, and injustice as
can be reached and regulated through legislation. … In order
to secure satisfactory results, it appears to your committee
imperatively necessary that the work shall be confined
strictly to the main purpose, viz, of ascertaining the nature
and effects of existing legislation, and the nature of
remedial legislation which may be necessary or desirable to
equalize conditions in industry and to remove any just grounds
of complaint on the part of either labor or capital or of the
people at large.
"To facilitate the progress of the work we recommend the

division of the Commission into four subcommissions of five
members each, to be severally charged with the investigation
of present conditions and the formulation of remedial
suggestions in the following branches of industry:
1. On agriculture and agricultural labor.
2. On the conditions of labor and capital employed in

manufacturing and general business.
3. On the conditions of labor and capital employed in mining.
4. On transportation.

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Practice Problem 8.1

The resulting products would be

The overall reaction mechanism would be

8-2 Copyright © 2018 Nelson Education Limited

Putting it all together would give the overall mechanism

Integrate the Skill 8.2

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Practice Problem 8.3

a) This alkene is asymmetric, so two possible carbocation intermediates can form.

8-4 Copyright © 2018 Nelson Education Limited

d) The asymmetric alkene has two possible intermediate carbocations.

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Integrate the Skill 8.4

8-6 Copyright © 2018 Nelson Education Limited

use most significant major product

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8-8 Copyright © 2018 Nelson Education Limited

resonance stabilized use most significant

Copyright © 2018 Nelson Education Limited 8-9

Substrate B also produces the desired molecule as the major product.

8-10 Copyright © 2018 Nelson Education Limited

So, compounds A and B would be the best molecules to use.

Practice Problem 8.7

a) Sulphuric acid is strong, so it will be completely dissociated in aqueous solution.

Water will then be the nucleophile reacting with the carbocation.

The protonated alcohol is deprotonated by water, regenerating the hydronium ion.

Copyright © 2018 Nelson Education Limited 8-11

Ethanol will then be the nucleophile reacting with the carbocation.

The protonated ether is deprotonated by alcohol regenerating the protonated alcohol.

8-12 Copyright © 2018 Nelson Education Limited

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Integrate the Skill 8.8

8-14 Copyright © 2018 Nelson Education Limited

The only regioisomer will be

b) Mercuric acetate reacts to form a symmetric intermediate.

Copyright © 2018 Nelson Education Limited 8-15

d) The initial product is asymmetric.

8-16 Copyright © 2018 Nelson Education Limited

Integrate the Skill 8.10

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Practice Problem 8.11

8-18 Copyright © 2018 Nelson Education Limited

Integrate the Skill 8.12

Reactions reversed to move from products to reactants.

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8-20 Copyright © 2018 Nelson Education Limited

Practice Problem 8.15

Any chiral molecules will be produced as racemic mixtures.