Ricardo Doroteo Manuel Grupo 43

REACCIONES CON FOSFORO

APPEL REACTION

The reaction of triphenylphosphine and tetrahalomethanes (CCl4, CBr4) with alcohols is a

ready method to convert an alcohol to the corresponding alkyl halide under mild conditions.
The yields are normally high.
This reaction is somewhat similar to the Mitsunobu Reaction, where the combination of a
phosphine, a diazo compound as a coupling reagent, and a nucleophile are used to invert
the stereochemistry of an alcohol or displace it.

Mechanism of the Appel Reaction

The reaction proceeds by activation of the triphenylphosphine by reaction with the
tetrahalomethane, followed by attack of the alcohol oxygen at phosphorus to generate an
oxyphosphonium intermediate. The oxygen is then transformed into a leaving group, and an
SN2 displacement by halide takes place, proceeding with inversion of configuration if the
carbon is asymmetric.
Ricardo Doroteo Manuel Grupo 43

MITSUNOBU REACTION

The Mitsunobu reaction is an organic reaction that converts an alcohol into a variety of

functional groups, such as an ester, using triphenylphosphine and an azodicarboxylate such
as diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD).[1] The
alcohol undergoes an inversion of stereochemistry. It was discovered by Oyo Mitsunobu
(1934–2003).

Reaction mechanism
The reaction mechanism of the Mitsunobu reaction is fairly complex. The identity of
intermediates and the roles they play has been the subject of debate.
Initially, the triphenyl phosphine (2) makes a nucleophilic attack upon diethyl
azodicarboxylate (1) producing a betaine intermediate 3, which deprotonates the carboxylic
acid (4) to form the ion pair 5. DEAD itself deprotonates the alcohol (6) forming an
alkoxide that can form the key oxyphosphonium ion 8. The ratio and interconversion of
intermediates 8 - 11 depend on the carboxylic acid pKa and the solvent polarity. [7][8]
[9]
 Although several phosphorus intermediates are present, the attack of the carboxylate
anion upon intermediate 8 is the only productive pathway forming the desired
product 12 and triphenylphosphine oxide (13).
Ricardo Doroteo Manuel Grupo 43

Hughes et al. have found that the formation of the ion pair 5 is very fast. The formation of
the oxyphosphonium intermediate 8 is slow and facilitated by the alkoxide. Therefore, the
overall rate of reaction is controlled by carboxylate basicity and solvation.
Ricardo Doroteo Manuel Grupo 43

WITTIG-HORNER REACTION
HORNER-WADSWORTH-EMMONS REACTION

The reaction of aldehydes or ketones with stabilized phosphorus ylides (phosphonate

carbanions) leads to olefins with excellent E-selectivity.

Mechanism of the Wittig-Horner Reaction

The reaction mechanism is similar to the mechanism of the Wittig Reaction. The

stereochemistry is set by steric approach control, where the antiperiplanar approach of the
carbanion to the carbon of the carbonyl group is favored when the smaller aldehydic
hydrogen eclipses the bulky phosphoranyl moiety. This places the ester group syn to the
aldehyde R group, but the incipient alkene assumes an E-orientation of these groups after
rotation to form the oxaphosphetane. As the lithium counterion does not interfere with
oxaphosphetane formation, use of BuLi is possible, but NaH and NaOMe are also suitable
bases for forming the ylide. The resulting phosphate byproduct is readily separated from the
desired products by simply washing with water.
Ricardo Doroteo Manuel Grupo 43

STAUDINGER REACTION
STAUDINGER REDUCTION

The Staudinger reaction is an

organic reaction used to convert an organic azide to a primary amine using a PR3 compound
(such as triphenylphosphine) and water. The mechanism begins with attack of the phos-
phorus on the far nitrogen of the organic azide to give a phosphazide intermediate. This
intermediate then goes through a rearrangement that releases a molecule of nitrogen gas
and forms a N-P ylide. The molecule of water then attacks the phosphorus atom and a
series or proton transfer steps follow to result in the formation of the final primary amine
and a triphenylphosphine oxide by-product.

Mecanismo

REACCIÓN DE HELL - VOLHARD - ZELINSKY

La reacción de Hell - Volhard - Zelinsky permite halogenar la posición a de los ácidos

carboxílicos.  Como reactivo se emplea bromo catalizado por fósforo.  El fósforo en
presencia de bromo genera tribromuro de fósforo que es en realidad el compuesto que actúa
de catalizador.
Ricardo Doroteo Manuel Grupo 43

El mecanismo de Hell - Volhard - Zelinsky transcurre en cuatro etapas

Etapa 1. Formación del bromuro de alcanoílo

Etapa 2. Enolización del haluro de alcanoílo

Etapa 3. Halogenación de la posición a

Etapa 4. Intercambio

REACTION MICHAELIS-ARBUZOV REACTION

The reaction of a trialkyl phosphite with an alkyl halide to produce an alkyl phosphonate.
The first step involves nucleophilic attack by the phosphorus on the alkyl halide, followed
by the halide ion dealkylation of the resulting trialkoxyphosphonium salt.
This reaction sees extensive application in the preparation of phosphonate esters for use in
the Horner-Emmons Reaction.
Ricardo Doroteo Manuel Grupo 43

Mechanism of the Arbuzov Reaction

VILSMEIER-HAACK REACTION

The Vilsmeier Reaction allows the formylation of electron-rich arenes.

Mechanism of the Vilsmeier-Haak Reaction

The formylating agent, also known as the Vilsmeyer-Haack Reagent, is formed in situ from
DMF and phosphorus oxychlorid:

An electrophilic aromatic substitution leads to α-chloro amines, which are rapidly

hydrolyzed during work up to give the aldehyde:
Ricardo Doroteo Manuel Grupo 43

Vilsmeier–Haack diformylation of 2-methylene-1,3-diselenole 140 gave 2-

diformylmethylene-1,3-diselenole 141, that served as a precursor for the dendralene-type
vinylogs of tetrathiafulvalene 1, 2, 39, 142, and 143 by condensation with suitable
dithiolium phosphonium salts or phosphonates in the presence of base <2001JOC7757>.

https://rodas5.us.es/items/d6c7060f-6906-4559-b7ed-97324cef2f0a/3/
https://www.quimicaorganica.org/acidos-carboxilicos/436-reaccion-de-hell-volhard-zelinsky.html
https://www.organic-chemistry.org/namedreactions/staudinger-reaction.shtm
https://enacademic.com/dic.nsf/enwiki/908129