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Basic organic name reaction

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BASIC ORGANIC
NAME
REACTION
 

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INDEX
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;ϰϲͿ <ŽůďĞʹ^ĐŚŵŝƚƚƌĞĂĐƚŝŽŶ      ϲϴ
;ϰϳͿ ůĂŝƐĞŶŽŶĚĞŶƐĂƚŝŽŶ       ϲϵ
;ϰϴͿ ^ƚŽďďĞĐŽŶĚĞŶƐĂƚŝŽŶ       ϳϬ
;ϰϵͿ ,ĞůůsŽůŚĂƌĚĞůŝŶƐŬLJZĞĂĐƚŝŽŶ;,sZĞĂĐƚŝŽŶͿ    ϳϭ
;ϱϬͿ ƚĂƌĚƌĞĂĐƚŝŽŶ        ϳϮ

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;ϭͿ :ŽŶĞƐKdžŝĚĂƚŝŽŶ




The Jones oxidation is an organic reaction for the oxidation of primary and
secondary alcohols to carboxylic acids and ketones, respectively. It is named after its
discoverer, Sir Ewart Jones.

Jones reagent consists of chromium trioxide and sulfuric acid dissolved in a mixture
of acetone and water. As an alternative, potassium dichromate can be used in place of
chromium trioxide. The oxidation is very rapid, quite exothermic, and the yields are
typically high. The reagent rarely oxidizes unsaturated bonds.

Application
Although useful reagent for some applications, due to the carcinogenic nature of
chromium(VI), the Jones oxidation has slowly been replaced by other oxidation
methods. It remains useful in organic synthesis. A variety of spectroscopic techniques,
including IR can be used to monitor the progress of a Jones oxidation reaction and
confirm the presence of the oxidized product. At one time the Jones oxidation was used
in primitive breathalyzers. Aminoindans, which are of pharmalogical interest, are
prepared by the oxidation of the alcohol to ketone which is converted into an amino
group. The alcohol is oxidized to the ketone with the Jones reagent. The reagent was
once used to prepare salicylic acid, a precursor to aspirin. Methcathinone is a
psychoactive stimulant that is sometimes used as an addictive recreational drug. It can
be oxidized from certain alcohols using the Jones reagent.

ϰ

 Related processes

Several other chromium compounds are used for the oxidation of alcohols.[3] These
include Collins reagent and pyridinium chlorochromate.The Sarett oxidation is a
similar process.

(2) Williamson Synthesis



The Williamson ether synthesis is an organic reaction, forming an ether from
an organohalide and a deprotonated alcohol (alkoxide). This reaction was developed
by Alexander Williamson in 1850.[2] Typically it involves the reaction of an alkoxide
ion with a primary alkyl halide via an SN2 reaction. This reaction is important in the
history of organic chemistry because it helped prove the structure of ethers.

Conditions

Since alkoxide ions are highly reactive, they are usually prepared immediately
prior to the reaction, or are generated in situ. In laboratory chemistry, in situ generation
is most often accomplished by the use of a carbonate base or potassium hydroxide,
while in industrial syntheses phase transfer catalysis is very common. A wide range of
solvents can be used, but protic solvents and apolar solvents tend to slow the reaction
rate strongly, as a result of lowering the availability of the free nucleophile. For this
reason, acetonitrile and N,N-dimethylformamide are particularly commonly used.
A typical Williamson reaction is conducted at 50 to 100 °C and is complete in
1 to 8 h. Often the complete disappearance of the starting material is difficult to achieve,

ϱ

 x In liquid ammonia alkali metals dissolve to give a blue solution thought of
simplistically as having "free electrons". The electrons are taken up by the
aromatic ring, one at a time. Once the first electron has been absorbed, a
radical anion has been formed. Next the alcohol molecule donates its
hydroxylic hydrogen to form a new C±H bond; at this point a radical has been
formed. This is followed by the second electron being picked up to give
a carbanion of the cyclohexadienyl type (i.e. with C=C±C±C=C in a six-
membered ring with negative charge). Then this cyclohexadienyl anion
is protonated by the alcohol present. The protonation takes place in the center
of the cyclohexadienyl system. This (regio-)selectivity is characteristic.
x Where the radical anion is initially protonated determines the structure of the
product. With an electron donor such as methoxy (MeO) or with an alkyl
group, protonation has been thought by some investigators as being ortho (i.e.
adjacent or 1,2) to the substituent. Other investigators have thought the
protonation is meta (1,3) to the substituent. Arthur Birch
favored meta protonation. With electron withdrawing substituents, protonation
has been thought to occur at the site of the substituent (ipso), or para (1,4).
Again, there has been varied opinion. A. J. Birch's empirical rules say that for
the donor substituents the final product has the maximum number of
substituents on the final double bonds. For electron withdrawing groups the
double bonds of the product avoid the substituents. The placement preference
of groups in the mechanism and in the final product is termed regioselectivity.
x reaction mechanism provides the details of molecular change as a reaction
proceeds. In the case of donating groups, A. J. Birch's preference
for meta protonation of the radical anion was based on qualitative reasoning,
but this has not been experimentally demonstrated.
x In 1961 a simple computation of the electron densities of the radical anion
revealed that it was the ortho site which was most negative and thus most
likely to protonate. Additionally, the second protonation was determined
computationally to occur in the center of the cyclohexadienyl anion to give an
unconjugated product.
x The uncertainty in the chemical literature is now only of historical
significance. Indeed, some further computational results have been reported,

ϭϭ

 which vary from suggesting a preference for meta radical-anion protonation to
suggesting a mixture of ortho and meta protonation.[citation needed]
x In 1990 and 1993 an esoteric test was devised which showed
that ortho protonation of the radical anion was preferred over meta (seven to
one).[citation needed] This was accompanied by more modern computation which
concurred. Both experiment and computations were in agreement with the
early 1961 computations.
x With electron withdrawing groups there are examples in the literature
demonstrating the nature of the carbanion just before final protonation,[citation
needed]
revealing that the initial radical-anion protonation occurs para to the
withdrawing substituent.
x The remaining item for discussion is the final protonation of the
cyclohexadienyl anion. In 1961 it was found that simple Hückel computations
were unable to distinguish between the different protonation sites.[citation
needed]
However, when the computations were modified with somewhat more
realistic assumptions, the Hückel computations revealed the center carbon to
the preferred. The more modern 1990 and 1993 computations were in
agreement.

ϭϮ

 (5) Diels-Alder reaction

In organic chemistry, the Diels±Alder reaction is a chemical reaction between

a conjugated diene and a substituted alkene, commonly termed the dienophile (also
spelled dieneophile), to form a substituted cyclohexene derivative. It is the prototypical
example of a pericyclic reaction with a concerted mechanism. More specifically, it is
classified as a thermally-allowed [4+2] cycloaddition with Woodward±Hoffmann
symbol >ʌs + ʌs]. It was first described by Otto Diels and Kurt Alder in 1928. For the
discovery of this reaction, they were awarded the Nobel Prize in Chemistry in 1950.
Through the simultaneous construction of two new carbon±carbon bonds, the Diels±
Alder reaction provides a reliable way to form six-membered rings with good control
over the regio- and stereochemical outcomes.[2][3] Consequently, it has served as a
powerful and widely applied tool for the introduction of chemical complexity in the
synthesis of natural products and new materials.[4][5] The underlying concept has also
EHHQDSSOLHGWRʌ-systems involving heteroatoms, such as carbonyls and imines, which
furnish the corresponding heterocycles; this variant is known as the hetero-Diels±Alder
reaction. The reaction has also been generalized to other ring sizes, although none of
these generalizations have matched the formation of six-membered rings in terms of
VFRSHRUYHUVDWLOLW\%HFDXVHRIWKHQHJDWLYHYDOXHVRIǻHƒDQGǻS° for a typical Diels±
Alder reaction, the microscopic reverse of a Diels±Alder reactions becomes favourable
at high temperatures, although this is of synthetic importance for only a limited range
of Diels-Alder adducts, generally with some special structural features; this reverse
reaction is known as the retro-Diels±Alder reaction.

ϭϯ

 involving X groups on both diene and dienophile, a 1,3-substitution pattern may be favored,
an outcome not accounted for by a simplistic resonance structure argument. However,
cases where the resonance argument and the matching of largest orbital coefficients
disagree are rare.

Stereospecificity and stereoselectivity

ls±Alder reactions, as concerted cycloadditions, are stereospecific. Stereochemical

information of the diene and the dienophile are retained in the product, as a syn addition
with respect to each component. For example, substituents in a cis (trans, resp.)
relationship on the double bond of the dienophile give rise to substituents that
are cis (trans, resp.) on those same carbons with respect to the cyclohexene ring.
Likewise, cis,cis- and trans,trans-disubstitued dienes give cis substituents at these
carbons of the product whereas cis,trans-disubstituted dienes give trans substituents:

ϭϱ

 (6) Ene reaction

The ene reaction (also known as the Alder-ene reaction by its discoverer Kurt Alder in
1943) is a chemical reaction between an alkene with an allylic hydrogen (the ene) and
a compound containing a multiple bond (the enophile), LQRUGHUWRIRUPDQHZı-bond
with migration of the ene double bond and 1,5 hydrogen shift. The product is a
substituted alkene with the double bond shifted to the allylic position.

This transformation is a group transfer pericyclic reaction,[2] and therefore, usually

requires highly activated substrates and/or high temperatures.[3] Nonetheless, the
reaction is compatible with a wide variety of functional groups that can be appended to
the ene and enophile moieties. Many useful Lewis acid-catalyzed ene reactions have
been also developed, which can afford high yields and selectivities at significantly
lower temperatures, making the ene reaction a useful C±C forming tool for the synthesis
of complex molecules and natural products.

ϭϲ

 (7) Ozonolysis

Ozonolysis is an organic reaction where the unsaturated bonds of alkenes, alkynes,

or azo compounds are cleaved with ozone. Alkenes and alkynes form organic
compounds in which the multiple carbon±carbon bond has been replaced by
a carbonyl group while azo compounds form nitrosamines. The outcome of the reaction
depends on the type of multiple bond being oxidized and the work-up conditions.



Ozonolysis of alkenes

Alkenes can be oxidized with ozone to form alcohols, aldehydes or ketones,

or carboxylic acids. In a typical procedure, ozone is bubbled through a solution of the
alkene in methanol DW í °C until the solution takes on a characteristic blue color,
which is due to unreacted ozone. This indicates complete consumption of the alkene.
Alternatively, various other chemicals can be used as indicators of this endpoint by
detecting the presence of ozone. If ozonolysis is performed by bubbling a stream of
ozone-enriched oxygen through the reaction mixture, the gas that bubbles out can be
directed through a potassium iodide solution. When the solution has stopped absorbing
ozone, the ozone in the bubbles oxidizes the iodide to iodine, which can easily be
observed by its violet color.[5] For closer control of the reaction itself, an indicator such
as Sudan Red III can be added to the reaction mixture. Ozone reacts with this indicator

ϭϳ

 more slowly than with the intended ozonolysis target. The ozonolysis of the indicator,
which causes a noticeable color change, only occurs once the desired target has been
consumed. If the substrate has two alkenes that react with ozone at different rates, one
can choose an indicator whose own oxidation rate is intermediate between them, and
therefore stop the reaction when only the most susceptible alkene in the substrate has
reacted.[6] Otherwise, the presence of unreacted ozone in solution (seeing its blue color)
or in the bubbles (via iodide detection) only indicates when all alkenes have reacted.
After completing the addition, a reagent is then added to convert the
intermediate ozonide to a carbonyl derivative. Reductive work-up conditions are far
more commonly used than oxidative conditions. The use
of triphenylphosphine, thiourea, zinc dust, or dimethyl sulfide produces aldehydes or
ketones while the use of sodium borohydride produces alcohols. The use of hydrogen
peroxide produces carboxylic acids. Recently, the use of amine N-oxides has been
reported to produce aldehydes directly.[7] Other functional groups, such
as benzyl ethers, can also be oxidized by ozone. It has been proposed that small
amounts of acid may be generated during the reaction from oxidation of the solvent,
so pyridine is sometimes used to buffer the reaction. Dichloromethane is often used as
a 1:1 cosolvent to facilitate timely cleavage of the ozonide. Azelaic acid and pelargonic
acids are produced from ozonolysis of oleic acid on an industrial scale.

(8) Simmons ± smith reaction

The Simmons±Smith reaction is an organic cheletropic reaction involving

an organozinc carbenoid that reacts with an alkene (or alkyne) to form
[1][2][3]
a cyclopropane. It is named after Howard Ensign Simmons, Jr. and Ronald D.
Smith. It uses a methylene free radical intermediate that is delivered to both carbons of
the alkene simultaneously, therefore the configuration of the double bond is preserved
in the product and the reaction is stereospecific.

ϭϴ

 


Limitations

ϭϵ

 
(9) Ziegler- Natta Catalyst

A Ziegler±Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used
in the synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of
Ziegler±Natta catalysts are employed, distinguished by their solubility:
x Heterogeneous supported catalysts based on titanium compounds are used in
polymerization reactions in combination with
cocatalysts, organoaluminium compounds such as triethylaluminium,
Al(C2H5)3. This class of catalyst dominates the industry.
x Homogeneous catalysts usually based on complexes of Ti, Zr or Hf. They are
usually used in combination with a different organoaluminium
cocatalyst, methyl aluminoxane (or methyl alumoxane, MAO). These catalysts
traditionally contains metallocene but also feature multidentate oxygen- and
nitrogen-based ligands.

ϮϬ

 Ziegler±Natta catalysts are used to polymerize terminal alkenes (ethylene and
alkenes with the vinyl double bond):









;ϭϬͿ Clemmensen Reduction


Clemmensen reduction is a chemical reaction described as a reduction of Ketones
(or aldehydes) to alkanes using zinc amalgam and concentrated hydrochloric acid.
This reaction is named after Erik Christian Clemmensen, a Danish chemist.


The original Clemmensen reduction conditions are particularly effective at
reducing aryl-alkyl ketones, such as those formed in a Friedel-Crafts acylation. The
two-step sequence of Friedel-Crafts acylation followed by Clemmensen reduction
constitutes a classical strategy for the primary alkylation of arenes. With aliphatic or

Ϯϭ

 cyclic ketones, modified Clemmensen conditions using activated zinc dust in an
anhydrous solution of hydrogen chloride in diethyl ether or acetic anhydride is much
more effective.
The substrate must be tolerant of the strongly acidic conditions of the Clemmensen
reduction (37% HCl). Several alternatives are available. Acid-sensitive substrates that
are stable to strong base can be reduced using the Wolff-Kishner reduction; a further,
milder method for substrates stable to hydrogenolysis in the presence of Raney
nickel is the two-step Mozingo reduction.
In spite of the antiquity of this reaction, the mechanism of the Clemmensen reduction
remains obscure. Due to the heterogeneous nature of the reaction, mechanistic studies
are difficult, and only a handful of studies have been disclosed.Mechanistic proposals
generally invoke organozinc intermediates, sometimes including zinc carbenoids,
either as discrete species or as organic fragments bound to the zinc metal surface.
However, the corresponding alcohol is believed not to be an intermediate, since
subjection of the alcohol to Clemmensen conditions generally does not afford the
alkane product.


(11) Baeyer villager oxidation

The Baeyer±Villiger oxidation is an organic reaction that forms an ester from

a ketone or a lactone from a cyclic ketone, using peroxyacids or peroxides as
the oxidant.[1] The reaction is named after Adolf von Baeyer and Victor Villiger who
first reported the reaction in 1899.

ϮϮ

 Mechanism






Condensation types

It is important to distinguish the aldol condensation from other addition reactions of

carbonyl compounds.
x When the base is an amine and the active hydrogen compound is sufficiently
activated the reaction is called a Knoevenagel condensation.
x In a Perkin reaction the aldehyde is aromatic and the enolate generated from
an anhydride.
x A Claisen condensation involves two ester compounds.

Ϯϱ

 x A Dieckmann condensation involves two ester groups in the same
molecule and yields a cyclic molecule
x A Henry reaction involves an aldehyde and an aliphatic nitro compound.
x A Robinson annulation LQYROYHVDQĮȕ-unsaturated ketone and
a carbonyl group, which first engage in a Michael reaction prior to the aldol
condensation.
x In the Guerbet reaction, an aldehyde, formed in situ from an alcohol, self-
condenses to the dimerized alcohol.
x In the Japp±Maitland condensation water is removed not by an elimination
reaction but by a nucleophilic displacement.


(13) Beckmann Reaction (rearrangement)

dŚĞĞĐŬŵĂŶŶ ƌĞĂƌƌĂŶŐĞŵĞŶƚ͕ ŶĂŵĞĚ ĂĨƚĞƌ ƚŚĞ 'ĞƌŵĂŶ ĐŚĞŵŝƐƚErnst Otto

Beckmann;ϭϴϱϯʹϭϵϮϯͿ͕ ŝƐ ĂrearrangementŽĨ ĂŶoximeĨƵŶĐƚŝŽŶĂů ŐƌŽƵƉ ƚŽ
ƐƵďƐƚŝƚƵƚĞĚamides͘dŚĞƌĞĂƌƌĂŶŐĞŵĞŶƚŚĂƐĂůƐŽďĞĞŶƐƵĐĐĞƐƐĨƵůƉĞƌĨŽƌŵĞĚŽŶŚĂůŽŝŵŝŶĞƐ
ĂŶĚnitrones͘LJĐůŝĐŽdžŝŵĞƐĂŶĚŚĂůŽŝŵŝŶĞƐLJŝĞůĚlactams͘
The Beckmann rearrangement is often catalyzed by acid, however other reagents have
been known to promote the rearrangement. These include tosyl chloride, thionyl
chloride, phosphorus pentachloride, phosphorus pentoxide, triethylamine, sodium
hydroxide, trimethylsilyl iodide among others. The Beckmann fragmentation is
another reaction that often competes with the rearrangement, though careful selection
of promoting reagent and solvent conditions can favor the formation of one over the
other, sometimes giving almost exclusively one product. The rearrangement
occurs stereospecifically for ketoximes and N-chloro/N-fluoro imines, with the
migrating group being anti-periplanar to the leaving group on the nitrogen. Certain
conditions have been known to racemize the oxime geometry, leading to the formation
of both regioisomers. The rearrangement of aldoximes occurs with stereospecificity in
the gas phase and without stereospecificity in the solution phase. A few methodologies
allow for the rearrangement of aldoximes to primary amides, but fragmentation
commonly competes in these systems. Nitrone rearrangement also occurs without

Ϯϲ

 (16) Schmidt Rearrangement

The Schmidt reaction is an organic reaction in which an azide reacts with a carbonyl group
to give an amine or amide, with expulsion of nitrogen. It is named after Sir Karl Friedrich
Schmidt.

(1)





(2)

ϯϭ

 (17) Claisen-Schmidt Condensation

dŚĞ ƌĞĂĐƚŝŽŶ ďĞƚǁĞĞŶ ĂŶ ĂůĚĞŚLJĚĞ Žƌ ŬĞƚŽŶĞ ŚĂǀŝŶŐ ĂŶ ĂůƉŚĂͲŚLJĚƌŽŐĞŶ ǁŝƚŚ ĂŶ ĂƌŽŵĂƚŝĐ
ĐĂƌďŽŶLJůĐŽŵƉŽƵŶĚůĂĐŬŝŶŐĂŶĂůƉŚĂŚLJĚƌŽŐĞŶŝƐĐĂůůĞĚƚŚĞůĂŝƐĞŶʹ^ĐŚŵŝĚƚĐŽŶĚĞŶƐĂƚŝŽŶ͘
/ŶĐĂƐĞƐǁŚĞƌĞƚŚĞƉƌŽĚƵĐƚĨŽƌŵĞĚƐƚŝůůŚĂƐƌĞĂĐƚŝǀĞĂůƉŚĂŚLJĚƌŽŐĞŶĂŶĚĂŚLJĚƌŽdžŝĚĞĂĚũĂĐĞŶƚ
ƚŽĂŶĂƌŽŵĂƚŝĐƌŝŶŐ͕ƚŚĞƌĞĂĐƚŝŽŶǁŝůůƋƵŝĐŬůLJƵŶĚĞƌŐŽĚĞŚLJĚƌĂƚŝŽŶůĞĂĚŝŶŐƚŽƚŚĞĐŽŶĚĞŶƐĂƚŝŽŶ
ƉƌŽĚƵĐƚ͘




ϯϮ

 (18) Dakin Reaction

Dakin Reaction is the replacement of the aldehyde group of ortho and para hydroxy
and ortho amino-benzaldehyde (or ketone) by a hydroxyl group on reaction with
alkaline hydrogen peroxide.

ϯϯ

 (19) Wolff Kishner Reduction Reaction

The reduction of aldehydes and ketones to alkanes. Condensation of the carbonyl

compound with hydrazine forms the hydrazone, and treatment with base induces the
reduction of the carbon coupled with oxidation of the hydrazine to gaseous nitrogen,
to yield the corresponding alkane.
Reaction of Aldehydes or Ketones with Hydrazine Produces a Hydrazone.

Reaction with a Base and Heat Converts a Hydrazone to an Alkane

(20) Favorskii rearrangement

The Favorskii rearrangement, named for the Russian chemist Alexei Yevgrafovich
Favorskii, is most principally a rearrangement of cyclopropanones and Į-halo
ketones which leads to carboxylic acid GHULYDWLYHV,QWKHFDVHRIF\FOLFĮ-halo ketones,
the Favorskii rearrangement constitutes a ring contraction. This rearrangement takes
place in the presence of a base, sometimes hydroxide, to yield a carboxylic acid but
most of the time either an alkoxide base or an amine to yield an ester or an amide,
UHVSHFWLYHO\ ĮĮ¶-Dihaloketones eliminate HX under the reaction conditions to give
Įȕ-unsaturated carbonyl compounds.

ϯϰ

 (23) Rosenmund reaction

The Rosenmund reduction is a hydrogenation process in which an acyl chloride is

selectively reduced to an aldehyde. The reaction was named after Karl Wilhelm
Rosenmund, who first reported it in 1918.

The reaction, a hydrogenolysis, is catalysed by palladium on barium sulfate, which is

sometimes called the Rosenmund catalyst. Barium sulfate has a low surface area which
reduces the activity of the palladium, preventing over-reduction. However, for certain
reactive acyl chlorides the activity must be reduced further, by the addition of a poison.
Originally this was thioquinanthrene although thiourea[2] has also been
used. Deactivation is required because the system must reduce the acyl chloride but not
the subsequent aldehyde. If further reduction does take place it will create a primary
alcohol which would then react with the remaining acyl chloride to form an ester.

ϯϳ

 (25) Pinacol-Pinacolone rearrangement

The pinacol±pinacolone rearrangement is a method for converting a 1,2-diol to

a carbonyl compound in organic chemistry. The 1,2-rearrangement takes place under
acidic conditions. The name of the rearrangement reaction comes from the
rearrangement of pinacol to pinacolone.

Mechanism

ϯϵ

 In the course of this organic reaction, protonation of one of the ±OH groups occurs and
a carbocation is formed. If both the ±OH groups are not alike, then the one which yields
a more stable carbocation participates in the reaction. Subsequently, an alkyl group
from the adjacent carbon migrates to the carbocation center. The driving force for this
rearrangement step is believed to be the relative stability of the resultant oxonium ion,
which has complete octet configuration at all centers (as opposed to the preceding
carbocation). The migration of alkyl groups in this reaction occurs in accordance with
their usual migratory aptitude, i.e.hydride > phenyl carbanion > tertiary carbanion
(if formed by migration) > secondary carbanion (if formed by migration) > methyl
carbanion . {Why Carbanion? Because every migratory group leaves by taking
electron pair with it.} The conclusion is that the group which stabilizes the carbocation
more effectively is migrated.

ϰϬ

 (26) Meerwein-Ponndorf-Verley (MPV) reduction

The Meerwein±Ponndorf±Verley (MPV) reduction in organic chemistry is

the reduction of ketones and aldehydes to their corresponding alcohols utilizing
aluminium alkoxide catalysis in the presence of a sacrificial alcohol.[1] The advantages
of the MPV reduction lie in its high chemoselectivity, and its use of a cheap
environmentally friendly metal catalyst.

The MPV reduction was discovered by Meerwein and Schmidt, and separately by
Verley in 1925. They found that a mixture of aluminium ethoxide and ethanol could
reduce aldehydes to their alcohols.[2][3] Ponndorf applied the reaction to ketones and
upgraded the catalyst to aluminium isopropoxide in isopropanol.

ϰϭ

 (28) 6\QWKHVLVRIDOGHK\GHE\6WHSKHQ¶VPHWKRG

Stephen aldehyde synthesis, a named reaction in chemistry, was invented by Henry

Stephen (OBE/MBE). This reaction involves the preparation of aldehydes (R-CHO)
from nitriles (R-CN) using tin(II) chloride (SnCl2), hydrochloric acid (HCl) and
quenching the resulting iminium salt ([R-CH=NH2]+Clí) with water (H2O).[1][2] During
the synthesis, ammonium chloride is also produced.

Mechanism

By addition of hydrogen chloride the used nitrile (1) reacts to its corresponding salt
(2). It is believed that this salt is reduced by a single electron transfer by the tin(II)
chloride (3a and 3b). The resulting salt (4) precipitates after some time as aldimine tin
chloride (5). Hydrolysis of 5 produces a amide (6) from which an aldehyde (7) is
formed.

Substitutes that increase the electron density promote the formation of the aldimin-tin
chloride adduct. By electron withdrawing substituents, the formation of amide
chloride is facilitated. In the past, the reaction was carried out by precipitating the
aldimine-tin chloride, washing it with ether and then hydrolyzing it. However, it has
been found that this step is unnecessary and the aldimine tin chloride can be
hydrolysed directly in the solution.

This reaction is more efficient when aromatic nitriles are used instead of aliphatic
ones. However, even for some aromatic nitriles (e. g. 2-formylbenzoic acid ethyl
ester) the yield can be low.

ϰϰ

 alkyl amine. However, aryl amines cannot be prepared via Gabriel synthesis as aryl
halides doQ¶WXQGHUJRVLPSOHQXFOHRSKLOLFVXEVWLWXWLRQ

Mechanism

Step 1

When potassium hydroxide is introduced to the phthalimide, an acid-base reaction

ensues. The hydroxide ion deprotonates the imide. The resulting proton is more acidic
than any simple amine (the two adjacent carbonyl-like groups offer resonance
stabilization), generating a strong nucleophile ± the imide ion.

Step 2

The nucleophilic imide ion attacks the electrophilic carbon of the alkyl halide. The
nitrogen atom subsequently replaces the halogen (Fluorine, Chlorine, Bromine or
Iodine) in the alkyl halide and bonds with the carbon itself. This results in the formation
of an N-Alkyl Phthalimide.

ϰϳ

 (33) Methylation by Diazomethane

Diazomethane is the chemical compound CH2N2, discovered by German chemist Hans

von Pechmann in 1894. It is the simplest diazo compound. In the pure form at room
temperature, it is an extremely sensitive explosive yellow gas; thus, it is almost
universally used as a solution in diethyl ether. The compound is a popular methylating
agent in the laboratory, but it is too hazardous to be employed on an industrial scale
without special precautions.[4] Use of diazomethane has been significantly reduced by
the introduction of the safer and equivalent reagent trimethylsilyldiazomethane.

Use

For safety and convenience diazomethane is always prepared as needed as a solution

in ether and used as such. It converts carboxylic acids into their methyl esters. The
reaction is thought to proceed via proton transfer from carboxylic acid to diazomethane
to give methyldiazonium cation, which immediately reacts with the carboxylate ion to
give the methyl ester and nitrogen gas. Since proton transfer is required and rate
limiting, this reaction exhibits high specificity for carboxylic acids over less acidic
oxygenated functional groups like alcohols and phenols.

ϱϬ

 Safety

Diazomethane is toxic by inhalation or by contact with the skin or eyes (TLV 0.2ppm).
Symptoms include chest discomfort, headache, weakness and, in severe cases,
collapse. Symptoms may be delayed. Deaths from diazomethane poisoning have been
reported. In one instance a laboratory worker consumed a hamburger near a fumehood
where he was generating a large quantity of diazomethane, and died four days later
from fulminating pneumonia.[15] Like any other alkylating agent it is expected to be
carcinogenic, but such concerns are overshadowed by its serious acute toxicity.

CH2N2 may explode in contact with sharp edges, such as ground-glass joints, even
scratches in glassware.[16] Glassware should be inspected before use and preparation
should take place behind a blast shield. Specialized kits to prepare diazomethane with
flame-polished joints are commercially available.

The compound explodes when heated beyond 100 °C, exposed to intense light, alkali
metals, or calcium sulfate. Use of a blast shield is highly recommended while using this
compound.

Proof-of-concept work has been done with microfluidics, in which continuous point-
of-use synthesis from N-methyl-N-nitrosourea and 0.93M potassium hydroxide in
water was followed by point-of-use conversion with benzoic acid, resulting in a 65%
yield of the methyl benzoate ester within seconds at temperatures ranging from 0-50 C.
The yield was better than under capillary conditions; the microfluidics were credited
with "suppression of hot spots, low holdup, isothermal conditions, and intensive
mixing."

(34) Paterno-Buchi Reaction

The Paternò±Büchi reaction, named after Emanuele Paternò and George Büchi who
established its basic utility and form, is a photochemical reaction that forms four-
membered oxetane rings from a carbonyl and an alkene.

ϱϭ

 The Ritter reaction is a chemical reaction that transforms a nitrile into an N-
alkyl amide using various electrophilic alkylating reagents. The original reaction
formed the alkylating agent using an alkene or alcohol in the presence of a strong
acid: The reaction has been the subject of several literature reviews.



Applications

The Ritter reaction is most useful in the formation of amides in which the nitrogen has
a tertiary alkyl group. It is also used in industrial processes as it can be effectively scaled
up from laboratory experiments to large-scale applications while maintaining high
yield. Real world applications include Merck's industrial-scale synthesis of anti-
HIV drug Crixivan (indinavir); the production of the falcipain-2 inhibitor PK-11195;
the synthesis of the alkaloid aristotelone; and synthesis of Amantadine, an antiviral and
antiparkinsonian drug. Other applications of the Ritter reaction include synthesis
of dopamine receptor ligands and licit and illicit production of racemic
amphetamine from allylbenzene and methyl cyanide.
A problem with the Ritter reaction is the necessity of an extremely strong
acid catalyst in order to produce the carbocation. This poses a safety risk when running
the reaction and makes disposal of waste products difficult. However, other methods
have been proposed in order promote carbocation formation, including
[19]
photocatalytic electron transfer or direct photolysis.

Example






ϱϰ

 



(37) Gatterman-Koch reaction

This reaction doesn't work on unactivated (even the least unactivated). For example,
we absolutely couldn't carry this reaction on a nitro-benzene. The utilization of
cuprous chloride isn't always necessary.

Mechanism

Step 1

Step 2

Step 3

ϱϱ

 Step 4

 

ϱϲ

 
(38) Reimer-Tiemann reaction

dŚĞZĞŝŵĞƌʹdŝĞŵĂŶŶ ƌĞĂĐƚŝŽŶŝƐ Ăchemical reactionƵƐĞĚ ĨŽƌ ƚŚĞorthoͲ

formylationŽĨphenols͖ǁŝƚŚ ƚŚĞ ƐŝŵƉůĞƐƚ ĞdžĂŵƉůĞ ďĞŝŶŐ ƚŚĞ ĐŽŶǀĞƌƐŝŽŶ
ŽĨphenolƚŽsalicylaldehyde͘ dŚĞ ƌĞĂĐƚŝŽŶ ǁĂƐ ĚŝƐĐŽǀĞƌĞĚ ďLJKarl
Reimer΀de΁ĂŶĚFerdinand Tiemann͘dŚĞZĞŝŵĞƌŝŶƋƵĞƐƚŝŽŶǁĂƐ<ĂƌůZĞŝŵĞƌ;ϭϴϰϱͲϭϴϴϯͿ
ŶŽƚƚŚĞůĞƐƐŬŶŽǁŶĂƌů>ƵĚǁŝŐZĞŝŵĞƌ;ϭϴϱϲͲϭϵϮϭͿ͘



Mechanism

Chloroform (1) is deprotonated by a strong base (normally hydroxide) to form the

chloroform carbanion (2) which will quickly alpha-eliminate to
give dichlorocarbene (3); this is the principal reactive species. The hydroxide will also
deprotonate the phenol (4) to give a negatively charged phenoxide (5). The negative
charge is delocalised into the aromatic ring, making it far more nucleophilic.
Nucleophilic attack of the dichlorocarbene gives an intermediate dichloromethyl
substituted phenol (7). After basic hydrolysis, the desired product (9) is formed.

ϱϳ

 (39) Ullmann synthesis

The Ullmann reaction or Ullmann coupling is a coupling reaction between aryl halides

and copper. The reaction is named after Fritz Ullmann.




Mechanism



ϱϴ

 (40) Wurtz- Fittig reaction

dŚĞtƵƌƚnjʹ&ŝƚƚŝŐ ƌĞĂĐƚŝŽŶŝƐ ƚŚĞchemical reactionŽĨaryl halidesǁŝƚŚalkyl

halidesĂŶĚsodiumŵĞƚĂů ŝŶ ƚŚĞ ƉƌĞƐĞŶĐĞ ŽĨ ĚƌLJ ĞƚŚĞƌ ƚŽ ŐŝǀĞ ƐƵďƐƚŝƚƵƚĞĚ ĂƌŽŵĂƚŝĐ
ĐŽŵƉŽƵŶĚƐ͘Charles Adolphe WurtzƌĞƉŽƌƚĞĚǁŚĂƚŝƐŶŽǁŬŶŽǁŶĂƐƚŚĞWurtz reactionŝŶ
ϭϴϱϱ͕ŝŶǀŽůǀŝŶŐ ƚŚĞ ĨŽƌŵĂƚŝŽŶ ŽĨ Ă ŶĞǁ ĐĂƌďŽŶͲĐĂƌďŽŶ ďŽŶĚ ďLJ ĐŽƵƉůŝŶŐ ƚǁŽ ĂůŬLJů ŚĂůŝĚĞƐ͘
tŽƌŬďLJWilhelm Rudolph FittigŝŶƚŚĞϭϴϲϬƐĞdžƚĞŶĚĞĚƚŚĞĂƉƉƌŽĂĐŚƚŽƚŚĞĐŽƵƉůŝŶŐŽĨĂŶ
ĂůŬLJů ŚĂůŝĚĞ ǁŝƚŚ ĂŶ ĂƌLJů ŚĂůŝĚĞ͘dŚŝƐ ŵŽĚŝĨŝĐĂƚŝŽŶ ŽĨ ƚŚĞ tƵƌƚnj ƌĞĂĐƚŝŽŶ ŝƐ ĐŽŶƐŝĚĞƌĞĚ Ă
ƐĞƉĂƌĂƚĞƉƌŽĐĞƐƐĂŶĚŝƐŶĂŵĞĚĨŽƌďŽƚŚƐĐŝĞŶƚŝƐƚƐ͘







The reaction works best for forming asymmetrical products if the halide reactants are
somehow separate in their relative chemical reactivities. One way to accomplish this is
to form the reactants with halogens of different periods. Typically the alkyl halide is
made more reactive than the aryl halide, increasing the probability that the alkyl halide
will form the organosodium bond first and thus act more effectively as
a nucleophile toward the aryl halide. Typically the reaction is used for the alkylation of
aryl halides; however, with the use of ultrasound the reaction can also be made useful
for the production of biphenyl compounds.

Mechanism

There are two approaches to describing the mechanism of the Wurtz±Fittig

reaction. The first involves the sodium-mediated formation of both alkyl and aryl
radicals. The alkyl and aryl radicals then combine to form a substituted aromatic
compound.

ϱϵ

 (41) Sandmeyer reaction

The Sandmeyer reaction is a chemical reaction used to synthesize aryl halides from
aryl diazonium salts using copper salts as reagents or catalysts. It is an example of
a radical-nucleophilic aromatic substitution. The Sandmeyer reaction provides a
method through which one can perform unique transformations on benzene, such
as halogenation, cyanation, trifluoromethylation, and hydroxylation.





ϲϬ

 (42) Claisen rearrangement

The Claisen rearrangement (not to be confused with the Claisen condensation) is a

powerful carbon±carbon bond-forming chemical reaction discovered by Rainer
Ludwig Claisen. The heating of an allyl vinyl ether will initiate a [3,3]-sigma tropic
rearrangement WRJLYHDȖį-unsaturated carbonyl.


The Claisen rearrangement is an exothermic, concerted (bond cleavage and
recombination) pericyclic reaction. Woodward±Hoffmann rules show a suprafacial,
stereospecific reaction pathway. The kinetics are of the first order and the whole
transformation proceeds through a highly ordered cyclic transition state and is
intramolecular. Crossover experiments eliminate the possibility of the rearrangement
occurring via an intermolecular reaction mechanism and are consistent with an
intramolecular process.
There are substantial solvent effects observed in the Claisen rearrangement, where
polar solvents tend to accelerate the reaction to a greater extent. Hydrogen-bonding
solvents gave the highest rate constants. For example, ethanol/water solvent mixtures
give rate constants 10-fold higher than sulfolane. Trivalent organoaluminium reagents,
such as trimethylaluminium, have been shown to accelerate this reaction.



(43) Fries rearrangement

The Fries rearrangement, named for the German chemist Karl Theophil Fries, is
a rearrangement reaction of a phenolic ester to a hydroxy aryl ketone
by catalysis of Lewis acids.
It involves migration of an acyl group of phenol ester to the aryl ring. The reaction
is ortho and para selective and one of the two products can be favoured by changing
reaction conditions, such as temperature and solvent.

ϲϰ

 substitution reaction is temperature dependent. A low reaction temperature favours para
substitution and with high temperatures the ortho product prevails, this can be
rationalised as exhibiting classic Thermodynamic versus kinetic reaction control as the
ortho product can form a more stable bidentate complex with the
Aluminium. Formation of the ortho product is also favoured in non-polar solvents; as
the solvent polarity increases, the ratio of the para product also increases.

(44) Bischler-Napieralski Reaction

The Bischler±Napieralski reaction is an intramolecular electrophilic aromatic

substitution reaction that allows for the cyclization RI ȕ-DU\OHWK\ODPLGHV RU ȕ-
arylethylcarbamates. It was first discovered in 1893 by August Bischler and Bernard
Napieralski, in affiliation with Basle Chemical Works and the University of Zurich.
The reaction is most notably used in the synthesis of dihydroisoquinolines, which can
be subsequently oxidized to isoquinolines.

Mechanisms

Two types of mechanisms have appeared in the literature for the Bischler±Napieralski
reaction. Mechanism I ŝŶǀŽůǀĞ a dichlorophosphoryl imine-ester intermediate, while
Mechanism II involves a nitrilium ion intermediate (both shown in brackets). This
mechanistic variance stems from the ambiguity over the timing for the elimination of
the carbonyl oxygen in the starting amide. In Mechanism I, the elimination occurs
with imine formation after cyclization; while in Mechanism II, the elimination yields
the nitrilium intermediate prior to cyclization. Currently, it is believed that different
reaction conditions affect the prevalence of one mechanism over the other
(see reaction conditions).
In certain literature, Mechanism II is augmented with the formation of an imidoyl
chloride intermediate produced by the substitution of chloride for the Lewis

ϲϲ

 Limitations
The Étard reaction is most commonly used as a relatively easy method of
converting toluene into benzaldehyde. Obtaining specific aldehyde products from
reagents other than toluene tends to be difficult due to rearrangements. For example, n-
propylbenzene is oxidized to propiophenone, benzyl methyl ketone, and several
chlorinated products, with benzyl methyl ketone being the major product. Another
example arises from the Étard reaction of trans-decalin which results in a mixture of
trans-9-decalol, spiro [4.5]decan-6-one, trans-1-decalone, cis-1-decalone, 9,10-octal-1-
one, and 1-tetralone.
Other oxidation reagents like potassium permanganate or potassium
dichromate oxidize to the more stable carboxylic acids.

Uses

Oxidation of toluene to benzaldehyde is quite a useful conversion. Benzaldehyde is

routinely used for its almond flavor. The aldehyde is comparatively reactive and readily
participates in aldol condensations. Benzaldehyde can serve as a precursor for various
compounds, including dyes, perfumes, and pharmaceuticals. For example, the first step
in the synthesis of ephedrine is condensation of benzaldehyde with nitroethane[citation
needed]
. Additionally, benzaldehyde is instrumental in the synthesis
of phentermine. Unlike other oxidising agents (like KMnO4 or CrO3 etc.), chromyl
chloride does not oxidise aldehyde to carboxylic acid.

ϳϯ

 Reference

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